Foam compositions and uses thereof

ABSTRACT

Components for articles of footwear and athletic equipment are provided including a foam. A variety of foams and foam components and compositions for forming the foams are provided. In some aspects, the foams and components including the foams can have exceptionally high energy return while also having improved durability and softness. In particular, midsoles including the foams are provided for use in an article of footwear. Methods of making the compositions and foams are provided, as well as methods of making an article of footwear including one of the foam components. In some aspects, the foams and foam components can be made by injection molding or injection molding followed by compression molding.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. patent applicationentitled “FOAM COMPOSITIONS AND USES THEREOF” having Ser. No. 15/833,276filed Dec. 6, 2017 which is a continuation of U.S. patent applicationentitled “FOAM COMPOSITIONS AND USES THEREOF” having Ser. No. 15/458,332filed Mar. 14, 2017, now U.S. Pat. No. 9,879,133, which claim priorityto, and the benefit of U.S. provisional application entitled “FOAMCOMPOSITIONS AND USES THEREOF” having Ser. No. 62/308,694 filed Mar. 15,2016, U.S. provisional application entitled “FOAM COMPOSITIONS AND USESTHEREOF” having Ser. No. 62/329,625 filed Apr. 29, 2016, and U.S.provisional application entitled “FOAM COMPOSITIONS AND USES THEREOF”having Ser. No. 62/429,912 filed Dec. 5, 2016, the contents of which areeach incorporated by reference in their entirety.

TECHNICAL FIELD

The present disclosure generally relates to materials, and in particularto materials for the footwear and related industries and uses thereof.

BACKGROUND

Footwear design involves a variety of factors from the aestheticaspects, to the comfort and feel, to the performance and durability.While footwear design and fashion may be rapidly changing, the demandfor increasing performance in the athletic footwear market isunchanging. To balance these demands, footwear designers employ avariety of materials and designs for the various components that make upan article of footwear.

BRIEF DESCRIPTION OF THE DRAWINGS

Further aspects of the present disclosure will be readily appreciatedupon review of the detailed description, described below, when taken inconjunction with the accompanying drawings.

FIG. 1 is an elevation view of an article of footwear with a solecomponent according to an aspect of the invention.

FIG. 2 is an exploded view of the sole component of the article offootwear of FIG. 1.

FIG. 3 is a plan view of the bottom of the sole component of the articleof footwear of FIG. 1.

FIG. 4 is a bottom view of an insert for use in a sole component of anarticle of footwear.

FIG. 5 is a top view of the insert of FIG. 4 inserted in a first portionto form a sole component.

DETAILED DESCRIPTION

New designs and materials for the footwear industry are needed. Inparticular, there remains a need for improved foam compositions, forexample that can be used in the footwear industry to provide improvedcushion and energy return when used in a midsole or other component foran article of footwear.

In various aspects, compositions are provided that can be foamed, i.e.can be used to produce a foam composition. For clarity, compositionsthat have not been foamed will, in some instances be referred to as“pre-foam” compositions. Foam compositions are also provided, e.g.compositions that have been prepared by foaming a “pre-foam” compositiondescribed herein. Articles of footwear, such as athletic shoes, andcomponents thereof are also provided including one or more of the foamcompositions. In particular, various aspects of the present disclosuredescribe sole components for an article of footwear having exceptionallyhigh energy return. The sole components having exceptionally high energyreturn can be made from foaming a pre-foam composition described herein.Methods of making the compositions and components made therefrom arealso provided.

Before the present disclosure is described in greater detail, it is tobe understood that this disclosure is not limited to particular aspectsdescribed, and as such may, of course, vary. Other systems, methods,features, and advantages of foam compositions and components thereofwill be or become apparent to one with skill in the art upon examinationof the following drawings and detailed description. It is intended thatall such additional systems, methods, features, and advantages beincluded within this description, be within the scope of the presentdisclosure, and be protected by the accompanying claims. It is also tobe understood that the terminology used herein is for the purpose ofdescribing particular aspects only, and is not intended to be limiting.The skilled artisan will recognize many variants and adaptations of theaspects described herein. These variants and adaptations are intended tobe included in the teachings of this disclosure and to be encompassed bythe claims herein.

Articles of Footwear

In various aspects, articles of footwear are provided. In particular,articles of footwear are provided including one or more components madeentirely or partially from a foam mentioned above and described in moredetail below. The foams and components made therefrom can have a rangeof desirable properties for footwear, including softness, durability,and an exceptionally high energy return. The articles of footwear can,in principal, include any article of footwear. In various aspects, thearticle of footwear can include a shoe, a boot, or a sandal.

The most common articles of footwear are shoes. Shoes can includeathletic shoes such as baseball shoes, basketball shoes, soccer shoes,football shoes, running shoes, cross-trainer shoes, cheerleading shoes,golf shoes, and the like. The shoes can, in some aspects, be cleated. Anexemplary article of footwear 10 is shown in FIG. 1. While an athleticshoe is exemplified in FIG. 1, it will be readily understood that someof the terminology employed will also apply to other articles offootwear or to other styles of shoe. Footwear 10 includes an upper 12and a sole component 14 secured to upper 12. Sole component 14 can be besecured to upper 12 by adhesive or any other suitable means. As usedherein, the sole component 14 can be a monolithic component formedentirely of the foam material as described herein, or a multi-componentassembly formed of a plurality of monolithic components, where at leastone of the monolithic components is formed entirely of the foam materialas described herein. Footwear 10 has a medial, or inner, side 16 and alateral, or outer, side 18.

The upper, in some aspects, is unformed until the point that it isattached to the sole component. In some aspects, the upper is a lastedupper. A “lasted upper,” as used herein, refers to an upper that isformed into the shoe shape prior to attachment to the sole by one ormore mechanical means. The lasted upper can include a heel counterformed to shape the heel of the upper. The lasted upper can include astrobel sock or a strobel board attached to the upper, typically via astrobel stitch.

Sole component 14, which is generally disposed between the foot of thewearer and the ground, provides attenuation of ground reaction forces(i.e., imparting cushioning), traction, and may control foot motions,such as pronation. As with conventional articles of footwear, solecomponent 14 can include an insole (not shown) located within upper 12.In some aspects, the sole component is an insole or sockliner or is amulti-component assembly including an insole or sockliner, can furtherinclude an insole or sockliner located within the upper, where theinsole or sockliner is formed entirely or partially of a foam materialdescribed herein. Articles of footwear described herein can include aninsole or sockliner formed entirely or partially of a foam materialdescribed herein.

The most common components of shoes and other footwear can be classifiedinto one of three types of components: upper components, lowercomponents, and grindery components. Upper components refer collectivelyto all of the components that are stitched or otherwise joined togetherto form the upper. The materials in the upper generally contribute tocharacteristics such as breathability, conformability, weight, andsuppleness or softness. The lower components refer collectively to allof the components that collectively form the lower. The lower caninclude, for example, the outsole and midsole. The choice of outsolematerials and design will contribute, for instance, to the durability,traction, as well as to the pressure distribution during use. Themidsole materials and design contribute to factors such as thecushioning and support. Grindery components include all of theadditional components that can be attached to the upper, lower, or both.Grindery components can include, for example, eyelets, toe puffs,shanks, nails, laces, velcro, catches, backers, linings, padding, heelbackings, heel foxings, toe caps, etc.

For purposes of general reference, footwear 10 can be divided into threegeneral portions: a forefoot portion 20, a midfoot portion 22, and aheel portion 24. Portions 20, 22, and 24 are not intended to demarcateprecise areas of footwear 10. Rather, portions 20, 22, and 24 areintended to represent general areas of footwear 10 that provide a frameof reference during the following discussion.

Unless otherwise stated, or otherwise clear from the context below,directional terms used herein, such as rearwardly, forwardly, top,bottom, inwardly, downwardly, upwardly, etc., refer to directionsrelative to footwear 10 itself. Footwear is shown in FIG. 1 to bedisposed substantially horizontally, as it would be positioned on ahorizontal surface when worn by a wearer. However, it is to beappreciated that footwear 10 need not be limited to such an orientation.Thus, in FIG. 1, rearwardly is toward heel portion 24, that is, to theright as seen in FIG. 1. Naturally, forwardly is toward forefoot portion20, that is, to the left as seen in FIG. 1, and downwardly is toward thebottom of the page as seen in FIG. 1. Top refers to elements toward thetop of the page as seen in FIG. 1, while bottom refers to elementstoward the bottom of the page as seen in FIG. 1. Inwardly is toward thecenter of footwear 10, and outwardly is toward the outer peripheral edgeof footwear 10.

Unless otherwise stated, or otherwise clear from the context below,directional terms used herein, such as rearwardly, forwardly, top,bottom, inwardly, downwardly, upwardly, etc., refer to directionsrelative to footwear 10 itself. Footwear is shown in FIG. 1 to bedisposed substantially horizontally, as it would be positioned on ahorizontal surface when worn by a wearer. However, it is to beappreciated that footwear 10 need not be limited to such an orientation.Thus, in FIG. 1, rearwardly is toward heel portion 24, that is, to theright as seen in FIG. 1. Naturally, forwardly is toward forefoot portion20, that is, to the left as seen in FIG. 1, and downwardly is toward thebottom of the page as seen in FIG. 1. Top refers to elements toward thetop of the page as seen in FIG. 1, while bottom refers to elementstoward the bottom of the page as seen in FIG. 1. Inwardly is toward thecenter of footwear 10, and outwardly is toward the outer peripheral edgeof footwear 10.

As can be seen in FIG. 2, sole component 14 consists of a first portion26 having an upper surface 27 with a recess 28 formed therein. Uppersurface 27 is secured to upper 12 with adhesive or other suitablefastening means. A plurality of substantially horizontal ribs 30 isformed on the exterior of first portion 26. In certain aspects, ribs 30extend from a central portion of forefoot portion 20 on medial side 16rearwardly along first portion 26, around heel portion 24 and forwardlyon lateral side 18 of first portion 26 to a central portion of forefootportion 20.

First portion 26 provides the external traction surface of solecomponent 14. In certain aspects it is to be appreciated that a separateoutsole component could be secured to the lower surface of first portion26.

Recess 28 extends from heel portion 24 to forefoot portion 20. Incertain aspects, the rear surface 32 of recess 28 is curved tosubstantially follow the contour of the rear of heel portion 24 and thefront surface 34 of recess 28 extends transversely across first portion26.

An insert 36 is received in recess 28. Insert 36 has a curved rearsurface 38 to mate with curved rear surface 32 of recess 28 and atransverse front surface 40 to mate with transverse front surface 34 ofrecess 28. An upper surface 42 of insert 36 is in contact with andsecured to upper 12 with adhesive or other suitable fastening means.

As seen best in FIG. 3, a ground engaging lower surface 44 of firstportion 26 includes a plurality of projections 46. Each projection 46 issurrounded by a groove 48. A plurality of transverse slots 50 are formedin lower surface 44, extending between adjacent projections 46. Alongitudinal slot 52 extends along lower surface 44 from heel portion 26to forefoot portion 20.

As illustrated in FIG. 2, insert 36 can provide cushioning or resiliencyin the sole component. First portion 26 can provide structure andsupport for insert 36. In such aspects, first portion 26 can be formedof a material of higher density and/or hardness as compared to insert 36such as, for example, non-foam materials including rubber andthermoplastic polyurethane, as well as foam materials. In certainaspects, insert 36 can be formed of a foam material as disclosed herein.

FIGS. 4 and 5 show bottom and top views of an insert 60 which can beused in a sole component as described herein. Insert 60 is similar toinsert 36, but as illustrated in FIGS. 4 and 5, insert 60 is formed oftwo types of materials 62 and 64, where at least one of the materials isa foam as disclosed herein. FIG. 4 shows a bottom view of insert 60,while FIG. 5 shows a top view of insert 60 formed of two types ofmaterials 62 and 64, with the insert placed inside a first portion 66 toform a sole component 14. Inserts with more than two types of materials,at least one of which is a foam as disclosed herein, can also be used.In the example illustrated in FIGS. 4 and 5, a portion of a firstmaterial 62 can be used in the heel region of the insert, and a portionof a second material 64 can be used in the toe region of the insert. Ahigher density material can be used to support the heel region, while alower density material can be used to support the toe region. Forexample, the density of the first material can be at least 0.02 g/cm³greater than the density of the second material. The shape of theportions of the two materials 62 and 64 of the insert can be anysuitable shape. For example, the heel region can be in the shape of awedge. Inserts formed of two types of materials can be useful in runningshoes, as well as in basketball shoes.

While the compositions and foams described herein can be used for makingany of a variety of components for an article of footwear, in particularaspects the components include a midsole, an outsole, an insole, atongue padding, a collar padding, and a combination thereof. In someaspects, the component is a sole component, such as a sole component 14depicted in FIGS. 1-5, that includes a foam described herein. In someaspects, the component is an insert such as insert 36 or insert 60depicted in FIGS. 4-5 that includes a foam described herein. The solecomponents and inserts for sole components can be made partially orentirely of a foam described herein. Any portion of a sole component oran insert for a sole component can be made of a foam described herein.For example, first portion 26 of the sole component (optionallyincluding the ground engaging lower surface 44, such as the plurality ofprojections 46 and/or the groove 48 surrounding the projections), theentire insert 36, portions 62 or 64 of insert 60, a separate outsolecomponent, or any combination thereof, can include a foam as describedherein. The sole components and inserts can be made by foaming acomposition provided herein, for example by injection molding or byinjection molding followed by compression molding as described herein.The foams and components can demonstrate improved physical propertiesincluding one or more of an enhanced energy return, and enhanced splittear, a decreased specific density, or a combination thereof.

Split tear is an important physical property for a foam for a componentof an article of footwear or athletic equipment. In some aspects, thefoam or component can have a split tear value of about 1.0 kg/cm to 4.5kg/cm, about 1.6 kg/cm to 4.0 kg/cm, about 2.0 kg/cm to 4.0 kg/cm, about2.0 kg/cm to 3.5 kg/cm, or about 2.5 kg/cm to 3.5 kg/cm. The split tearcan be measured as described in the examples below. In some aspects, thefoam or component is compression molded, and the compression molded foamor component can have a split tear of about 0.08 kg/cm to 4.0 kg/cm,about 0.9 kg/cm to 3.0 kg/cm, about 1.0 to 2.0 kg/cm, about 1.0 kg/cm to1.5 kg/cm, or about 2 kg/cm. In some aspects, the foam or component isinjection molded, and the foam or component can have a split tear ofabout 0.07 kg/cm to 2.0 kg/cm, or about 0.8 kg/cm to 1.5 kg/cm, or about0.9 to 1.2 kg/cm, about 1.5 kg/cm to 2.2 kg/cm.

The energy return, a measure of the percentage of energy the foam orcomponent returns when compressed, is an important physical property.This is especially true for running and other athletic shoes. In someaspects, the foams and components provided herein have an energy returnof about 60% to 90%, about 60% to 85%, about 65% to 85%, or about 70% to85%. In some aspects, the foam or component is compression molded andcan have an energy return of about 60% to 95% (e.g., about 60% to 85%;about 65% to 80%; about 65% to 75%; about 70% to 80%; or about 75% to80%; about 75% to 85%; about 80% to 95%; or about 85% to 95%). Theenergy return can be measured as described in the examples below.

The foams and components can be lightweight. In some aspects, the foamsand components can have a specific density of about 0.05 to 0.25, about0.05 to 0.2, about 0.05 to 0.15, about 0.08 to 0.15, about 0.08 to 0.20,about 0.08 to 0.25, or about 0.1 to 0.15. In some aspects the foam orcomponent is compression molded and can have a specific density of about0.15 to 0.3, about 0.2 to 0.3, or about 0.15 to 0.25.

In some examples, the process for making the foams and components of thevarious examples described herein further includes compression moldingthe foam to give a compression molded foam or a compression moldedcomponent. In some aspects, compression molding foamed preforms formedfrom the foam compositions of the present disclosure can producecompression molded foam components having physical properties which makethese components particularly advantageous for use in articles offootwear and athletic equipment. For example, the physical properties ofthese compression molded foam components make them particularly usefulfor use as cushioning elements, such as midsoles.

In some aspects, the resiliency and/or energy return of the compressionmolded foam or compression molded component can be significantly greaterthan the resiliency and/or energy return of the otherwise same foampreform used to make the compression molded foam component. Whilecompression molded foam components formed from preforms foamed usingother blowing methods sometimes have greater resiliency and/or energyreturn than their preforms, an even greater increase in resiliencyand/or energy return can be achieved when compression molding foampreforms that were foamed using an impregnation process utilizing aphysical blowing agent, as described herein. The resiliency and/orenergy return of the compression molded foam component can be at leastat least 6 percentage points, or at least 7 percentage points, or atleast 8 percentage points, or at least 9 percentage points, or at least10 percentage points, or at least 12 percentage points greater than theresiliency and/or energy return of the foam preform used to make thecompression molded foam component. In particular examples, theresiliency and/or energy return of the compression molded foam componentis at least 9 percentage points greater than the resiliency and/orenergy return of the foam preform used for make the compression moldedfoam component.

This greater increase in the resiliency and/or energy return of thecompression molded foam component can thus result in components havinghigher resiliency and/or energy return than would be possible using foampreforms made using other blowing methods. Using the blowing methodsdescribed herein, it has been found that it is possible to producecompression molded foam components having higher than usual resiliencieswhile using materials and methods which are cost-effective for use inconsumer goods such as articles of footwear and athletic equipment. Theresiliency and/or energy return of the compression molded foam componentcan be greater than 45%, or greater than 50%, or greater than 55%, orgreater than 60%, or greater than 65%. For example, the resiliencyand/or energy return of the compression molded foam component can befrom 45% to 95%, or from 50% to 90%, or from 55% to 90%, or from 60% to80%, or from 50% to 85%, or from 55% to 75%, or from 60% to 75%.Compression molded foam components having resiliencies greater than 45%,or 50%, or 55%, or 60%, or 65%, can be particularly advantageous for usein articles of footwear. Additionally or in combination, the resiliencyand/or energy return of the foam preform can be less than 75%, or lessthan 70%, or less than 65%, or less than 60%. For example, theresiliency and/or energy return of the foam preform can be from 40% to80%, or from 55% to 75%, or from 50% to 70% or from 65% to 80%.

In particular examples, the resiliency and/or energy return of thecompression molded foam component can be at least at least 6 percentagepoints, or at least 7 percentage points, or at least 8 percentagepoints, or at least 9 percentage points, or at least 10 percentagepoints, or at least 12 percentage points greater than the resiliencyand/or energy return of the foam preform used to make the compressionmolded foam component when the compression molded foam component has aresiliency and/or energy return greater than 45%, or greater than 50%,or greater than 55%, or greater than 60%, or greater than 65%.

Several methods of measuring resiliency and/or energy return of foams(e.g., foam preforms and foam components) exist in the art. One methodof measuring resiliency of foams is based on ASTM D 2632-92, which is atest for solid rubber materials. For use with foams, the test sample isprepared as described in ASTM D2632-92, but uses a sample of foam inplace of the sample of solid rubber. This test uses a plunger which isdropped from a height onto a test sample while being guided by avertical rod. The drop height is divided into 100 equal parts, and theheight to which the plunger rebounds is measured using this 100 partscale, to determine the resiliency of the sample. Alternative methodswhich use a ball of standard weight dropped onto a sample, and whichmeasure the rebound height of the ball to determine the resiliency ofthe sample can also be used.

The specific gravity of a foam is also an important physical property toconsider when using a foam for a component of an article of footwear orathletic equipment. The foams and components of the present disclosurecan have a specific gravity of from 0.02 g/cm³ to 0.22 g/cm³, or of from0.03 g/cm³ to 0.12 g/cm³, or of from 0.04 g/cm³ to 0.10 g/cm³, or from0.11 g/cm³ to 0.12 g/cm³, or from 0.10 g/cm³ to 0.12 g/cm³, from 0.15g/cm³ to 0.2 g/cm³; 0.15 g/cm³ to 0.30 g/cm³. Alternatively or inaddition, the foam preform can have a specific gravity of from 0.01g/cm³ to 0.10 g/cm³, or of from 0.02 g/cm³ to 0.08 g/cm³, or of from0.03 g/cm³ to 0.06 g/cm³; 0.08 g/cm³ to 0.15 g/cm³; or from 0.10 g/cm³to 0.12 g/cm³. For example, the specific gravity of the compressionmolded foam component can be from or from 0.15 g/cm³ to 0.2 g/cm³, andthe specific gravity of the foam preform can be from 0.10 g/cm³ to 0.12g/cm³. The foam or component can be compression molded.

In particular examples, the resiliency and/or energy return of thecompression molded foam component can be at least at least 6 percentagepoints, or at least 7 percentage points, or at least 8 percentagepoints, or at least 9 percentage points, or at least 10 percentagepoints, or at least 12 percentage points greater than the resiliencyand/or energy return of the foam preform used to make the compressionmolded foam component when the compression molded foam component has aresiliency and/or energy return greater than 45%, or greater than 50%,or greater than 55%, or greater than 60%, or greater than 65%, and thecompression molded foam can have a specific gravity of from 0.02 g/cm³to 0.15 g/cm³, or of from 0.03 g/cm³ to 0.12 g/cm³, or of from 0.04g/cm³ to 0.10 g/cm³ or from 0.11 g/cm³ to 0.12 g/cm³, from 0.15 g/cm³ to0.2 g/cm³; or 0.15 g/cm³ to 0.30 g/cm³.

The specific gravity of the foam or component can be determined bytesting at least 3 representative samples taken from a foam preform orcompression molded foam component (e.g., a 2 inch×2 inch sample or a 1inch×1 inch sample), or at least 3 entire foam preforms or compressionmolded foam components. Using a balance with appropriate accuracy forthe weight of the sample, the weight of each sample is determined bothin air and when the sample is completely submerged in distilled water ata temperature of 22° C.±2° C., after removing any air bubbles adhered tothe surface of the foam sample weighing. The specific gravity (S.G.) isthen calculated by taking the weight of the sample in water andsubtracting that from the weight of the sample in air, and this value isthen divided into the weight of the sample in air, where all the weightsare weights in grams.

Compression set of a foam is another important physical property for afoam used as a component of an article of footwear or athleticequipment. In accordance with the present disclosure, the compressionmolded foam or compression molded component can have a compression setof from 40% to 100%. For example, the compression set can be from 45% to90%, or from 40% to 80%, or from 50% to 75%.

Compression set can be measured by preparing a sample of a standardthickness (e.g., 10 mm) of a foam preform. Components having a thicknessless than the standard can be stacked to make a sample having thestandard thickness. The sample is loaded into a metal compression plateand compressed to a height of 50% of the original thickness (e.g., 5mm). The sample is placed in a 50° C. oven on its side for 6 hours. Atthe end of the 6 hours, the sample is removed from the oven and from themetal compression plate, and allowed to cool for 30 minutes. Oncecooled, the thickness of the sample is measured. The percent compressionset (C.S.) is calculated by (a) subtracting the final sample thicknessfrom the original sample thickness, and (b) subtracting the 50%compressed thickness from the original sample thickness, (c) dividing(a) by (b), and (d) multiplying the result by 100 to obtain the percentcompression set (where all thicknesses are measured in millimeters).

Durometer is another important physical property of a foam or componentthat is to be used in an article of footwear or athletic equipment. Inaccordance with the present disclosure, the compression molded foam orcomponent can have a durometer of at least 20 Asker C, or at least 30Asker C, or at least 40 Asker C, or at least 50 Asker C. For example,the durometer of the compression molded foam or compression moldedcomponent can have a durometer of from 20 Asker C to 70 Asker C, or offrom 20 Asker C to 40 Asker C, or from 30 Asker C to 35 Asker C, or offrom 25 Asker C to 65 Asker C, or of from 30 Asker C to 50 Asker C, orof from 40 Asker C to 70 Asker C, or of from 35 Asker C to 55 Asker C,or from 50 Asker C to 65 Asker C. The foam preform can have a durometerof less than 40 Asker C, or less than 30 Asker C, or less than 20 AskerC. For example, the durometer of the foam preform can be from 15 Asker Cto 50 Asker C, or from 20 Asker C to 50 Asker C, or from 20 Asker C to40 Asker C, or from 20 Asker C to 30 Asker C. The durometer can bemeasured on a flat area of foam, e.g., at least 6 mm thick using anAsker C durometer.

In particular examples, the resiliency and/or energy return of thecompression molded foam component can be at least at least 6 percentagepoints, or at least 7 percentage points, or at least 8 percentagepoints, or at least 9 percentage points, or at least 10 percentagepoints, or at least 12 percentage points greater than the resiliencyand/or energy return of the foam preform used to make the compressionmolded foam component when the compression molded foam component has aresiliency and/or energy return greater than 45%, or greater than 50%,or greater than 55%, or greater than 60%, or greater than 65%, and thecompression molded foam component can have a of at least 20 Asker C, orat least 30 Asker C, or at least 40 Asker C, or at least 50 Asker C. Inaddition, the compression molded foam can have a specific gravity offrom 0.02 g/cm³ to 0.15 g/cm³, or of from 0.03 g/cm³ to 0.12 g/cm³, orof from 0.04 g/cm³ to 0.10 g/cm³, or from 0.11 g/cm³ to 0.12 g/cm³ from0.15 g/cm³ to 0.2 g/cm³; or 0.15 g/cm³ to 0.30 g/cm³.

Split tear is another important physical property for a foam or acomponent used in an article of footwear or athletic equipment. Inaccordance with the present disclosure, the compression molded foam orcomponent can have a split tear of from 0.08 kg/cm to 4.0 kg/cm, or offrom 0.9 kg/cm to 3.0 kg/cm, or of from 1.0 to 2.0 kg/cm, or of from 1.0kg/cm to 1.5 kg/cm, or of about 2 kg/cm. Alternatively or in addition,the foam preform can have a split tear of from 0.07 kg/cm to 2.0 kg/cm,or of from 0.8 kg/cm to 1.5 kg/cm, or of from 0.9 to 1.2 kg/cm, or fromabout 1.5 kg/cm to about 2.2 kg/cm.

Split tear for foam preforms and compression molded foam components canbe measured using ASTM D3574-95. Although this method is directed tobonded and molded urethane foams, it can be used on any foam material inaccordance with the present disclosure. A sample of foam having athickness of 10 mm±1 mm. If the foam preform or compression molded foamcomponent has an outer skin, the outer skin should not be present on thetest sample. A 3 cm long cut is placed in the center of one end of thespecimen, and marked in five successive 2 cm portions along the edge ofthe sample. The sample is tested as described in ASTM D3574-95.

The tear strength of the compression molded foam component can rangefrom 4 kg/cm to 10 kg/cm.

The tensile strength of the foam is another important physicalcharacteristic. The foam or component can have a tensile strength offrom 5 kg/cm² to 25 kg/cm², or of from 10 kg/cm² to 23 kg/cm², or offrom 15 kg/cm² to 22 kg/cm². The tensile strength can be measured on adie cut sample of the foam in the shape of a dumbbell of a standard sizesuch as a 2.5 cm in width by 11.5 cm in length, with a minimum thicknessof 3 to 4 mm. The dumbbell follows the shape described in ASTM D412, dieC. The sample is loaded symmetrically into and tested using a longtravel extensometer such as the Instron 2603-080 which allows for aminimum of 1000% strain with a gauge length of 25 mm and a resolution ofat least 0.1 mm. The tensile value at the failure point of the sample(the point during testing when the load value initially drops) isrecorded. The foam or component can be compression molded.

Another physical property to consider when determining whether or not afoam is suitable for use as a component of an article of footwear orathletic equipment is its 300% elongation. The compression molded foamor component can have an elongation of at least 125 kg/cm², or at least150 kg/cm².

Some examples described herein are directed to a foam article (e.g.,articles used to make at least portions of footwear or athleticequipment) made by a process/method comprising: forming a pre-foamcomposition comprising a polymer comprising styrene repeating units andnon-styrenic repeating units; and a C₄-C₁₀₀ unsaturated olefin;crosslinking the polymer comprising styrene repeating units andnon-styrenic repeating units and the C₄-C₁₀₀ unsaturated olefin olefinblock copolymer of the pre-foam composition, forming a crosslinkedpre-foam composition; and blowing the pre-foam composition, thecrosslinked pre-foam composition, or blowing both the pre-foamcomposition and the crosslinked pre-foam composition, to give a foamarticle. In some examples, the cross-linking and the blowing can occursubstantially simultaneously. In some examples, the process for formingfoam articles further comprises injection molding the pre-foamcomposition, and the crosslinking occurs during the injection molding.In some examples, the crosslinked composition, or both the pre-foamcomposition and the crosslinked composition are blown in a mold. In someexamples, the crosslinking occurs during the injection molding (e.g.,the crosslinking occurs substantially in the mold).

In some examples, the foam articles of the various examples describedherein can further comprise at least one ethylene vinyl acetatecopolymer and/or at least one olefin block copolymer, as each of theterms is defined herein. The component, such as the midsole, can have avariety of beneficial properties.

It has been found that, for many examples, the resiliency and/or energyreturn (also referred to as energy return) of the compression moldedfoam article can be significantly greater than the resiliency and/orenergy return of the foam article used to make the compression moldedfoam article. While compression molded foam articles formed using otherblowing methods sometimes have greater resiliency and/or energy returnthan the corresponding foam article, an even greater increase inresiliency and/or energy return can be achieved when compression moldingfoam articles that were foamed using an impregnation process utilizing aphysical blowing agent, as described herein. The resiliency and/orenergy return of the compression molded foam article can be at least atleast 6 percentage points, or at least 7 percentage points, or at least8 percentage points, or at least 9 percentage points, or at least 10percentage points, or at least 12 percentage points greater than theresiliency and/or energy return of the foam article used to make thecompression molded foam article. In particular examples, the resiliencyand/or energy return of the compression molded foam article is at least9 percentage points greater than the resiliency and/or energy return ofthe foam article used for make the compression molded foam article.

This greater increase in the resiliency and/or energy return of thecompression molded foam article can thus result in components havinghigher resiliency and/or energy return than would be possible using foamarticles made using other blowing methods. Using the blowing methodsdescribed herein, it has been found that it is possible to producecompression molded foam articles having higher than usual resiliencieswhile using materials and methods which are cost-effective for use inconsumer goods such as articles of footwear and athletic equipment. Theresiliency and/or energy return of the compression molded foam articlecan be greater than 45%, or greater than 50%, or greater than 55%, orgreater than 60%, or greater than 65%. For example, the resiliencyand/or energy return of the compression molded foam article can be from45% to 95%, or from 50% to 90%, or from 55% to 90%, or from 60% to 80%,or from 50% to 85%, or from 55% to 75%, or from 60% to 75%. Compressionmolded foam articles having resiliencies greater than 45%, or 50%, or55%, or 60%, or 65%, can be particularly advantageous for use inarticles of footwear. Additionally or in combination, the resiliencyand/or energy return of the foam article can be less than 75%, or lessthan 70%, or less than 65%, or less than 60%. For example, theresiliency and/or energy return of the foam article can be from 40% to80%, or from 55% to 75%, or from 50% to 70% or from 65% to 80%.

In particular examples, the resiliency and/or energy return of thecompression molded foam article can be at least at least 6 percentagepoints, or at least 7 percentage points, or at least 8 percentagepoints, or at least 9 percentage points, or at least 10 percentagepoints, or at least 12 percentage points greater than the resiliencyand/or energy return of the foam article used to make the compressionmolded foam article when the compression molded foam article has aresiliency and/or energy return greater than 45%, or greater than 50%,or greater than 55%, or greater than 60%, or greater than 65%.

The specific gravity of a foam article is also an important physicalproperty to consider when using a foam for a component of an article offootwear or athletic equipment. The compression molded foam articles ofthe present disclosure can have a specific gravity of from 0.02 g/cm³ to0.22 g/cm³, or of from 0.03 g/cm³ to 0.12 g/cm³, or of from 0.04 g/cm³to 0.10 g/cm³, or from 0.11 g/cm³ to 0.12 g/cm³, or from 0.10 g/cm³ to0.12 g/cm³, from 0.15 g/cm³ to 0.2 g/cm³; 0.15 g/cm³ to 0.30 g/cm³.Alternatively or in addition, the foam article can have a specificgravity of from 0.01 g/cm³ to 0.10 g/cm³, or of from 0.02 g/cm³ to 0.08g/cm³, or of from 0.03 g/cm³ to 0.06 g/cm³; 0.08 g/cm³ to 0.15 g/cm³; orfrom 0.10 g/cm³ to 0.12 g/cm³. For example, the specific gravity of thecompression molded foam article can be from or from 0.15 g/cm³ to 0.2g/cm³, and the specific gravity of the foam article can be from 0.10g/cm³ to 0.12 g/cm³.

In particular examples, the resiliency and/or energy return of thecompression molded foam article can be at least at least 6 percentagepoints, or at least 7 percentage points, or at least 8 percentagepoints, or at least 9 percentage points, or at least 10 percentagepoints, or at least 12 percentage points greater than the resiliencyand/or energy return of the foam article used to make the compressionmolded foam article when the compression molded foam article has aresiliency and/or energy return greater than 45%, or greater than 50%,or greater than 55%, or greater than 60%, or greater than 65%, and thecompression molded foam article can have a specific gravity of from 0.02g/cm³ to 0.15 g/cm³, or of from 0.03 g/cm³ to 0.12 g/cm³, or of from0.04 g/cm³ to 0.10 g/cm³, or from 0.11 g/cm³ to 0.12 g/cm³ from 0.15g/cm³ to 0.2 g/cm³; or 0.15 g/cm³ to 0.30 g/cm³.

Compression set of a foam article is another important physical propertyfor a foam used as a component of an article of footwear or athleticequipment. In accordance with the present disclosure, the compressionmolded foam article can have a compression set of from 40% to 100%. Forexample, the compression set can be from 45% to 90%, or from 40% to 80%,or from 50% to 75%.

Durometer is another important physical property of a foam article usedas an article of footwear or athletic equipment. In accordance with thepresent disclosure, the compression molded foam article can have adurometer of at least 20 Asker C, or at least 30 Asker C, or at least 40Asker C, or at least 50 Asker C. For example, the durometer of thecompression molded foam article can have a durometer of from 20 Asker Cto 70 Asker C, or of from 20 Asker C to 40 Asker C, or from 30 Asker Cto 35 Asker C, or of from 25 Asker C to 65 Asker C, or of from 30 AskerC to 50 Asker C, or of from 40 Asker C to 70 Asker C, or of from 35Asker C to 55 Asker C, or from 50 Asker C to 65 Asker C. The foamarticle can have a durometer of less than 40 Asker C, or less than 30Asker C, or less than 20 Asker C. For example, the durometer of the foampreform can be from 15 Asker C to 50 Asker C, or from 20 Asker C to 50Asker C, or from 20 Asker C to 40 Asker C, or from 20 Asker C to 30Asker C. The durometer can be measured on a flat area of foam, e.g., atleast 6 mm thick using an Asker C durometer.

In particular examples, the resiliency and/or energy return of thecompression molded foam article can be at least at least 6 percentagepoints, or at least 7 percentage points, or at least 8 percentagepoints, or at least 9 percentage points, or at least 10 percentagepoints, or at least 12 percentage points greater than the resiliencyand/or energy return of the foam article used to make the compressionmolded foam article when the compression molded foam article has aresiliency and/or energy return greater than 45%, or greater than 50%,or greater than 55%, or greater than 60%, or greater than 65%, and thecompression molded foam article can have a of at least 20 Asker C, or atleast 30 Asker C, or at least 40 Asker C, or at least 50 Asker C. Inaddition, the compression molded foam article can have a specificgravity of from 0.02 g/cm³ to 0.15 g/cm³, or of from 0.03 g/cm³ to 0.12g/cm³, or of from 0.04 g/cm³ to 0.10 g/cm³, or from 0.11 g/cm³ to 0.12g/cm³ from 0.15 g/cm³ to 0.2 g/cm³; or 0.15 g/cm³ to 0.30 g/cm³.

The tear strength of the compression molded foam or article can rangefrom 4 kg/cm to 10 kg/cm. The tensile strength of the foam or article isanother important physical characteristic. The compression molded foamarticle can have a tensile strength of from 5 kg/cm² to 25 kg/cm², or offrom 10 kg/cm² to 23 kg/cm², or of from 15 kg/cm² to 22 kg/cm².

Another physical property to consider when determining whether or not afoam article is suitable for use as a component of an article offootwear or athletic equipment is its 300% elongation. The compressionmolded foam article can have an elongation of at least 125 kg/cm², or atleast 150 kg/cm².

Various examples include methods of manufacturing an article of footwearor components for an article of footwear. In some examples, the methodsof manufacturing an article of footwear include blowing a compositiondescribed herein to give a foam article; compression molding the foamarticle to make a compression molded component for an article offootwear. The component can be a midsole, and the method can includeproviding an upper and an outsole for an article of footwear; andcombining the compression molded midsole, the upper, and the outsole tomake an article of footwear. In some examples, the method ofmanufacturing the article of footwear includes combining a compressionmolded foam article, an upper, and an outsole to make an article offootwear.

In some aspects, the present disclosure is directed to a compressionmolded foam, and to a method of forming compression molded foam for,among other applications, articles of footwear or athletic equipment. Insome examples, the method can be a process comprising providing (e.g.,preparing) a foam preform and then compression molding the foam preformto form a compression molded foam.

The present inventors have recognized, among other things, that thecompression molded foam of the various examples described herein hasimproved physical characteristics, such as, for example, improvedresiliency and/or energy return.

In some examples, one step of the method comprises providing (e.g.,preparing or obtaining) a pre-foam composition as disclosed herein. Forexample, the pre-foam composition can be prepared using any method knownin the art, including using a suitable kneader, a suitable single-screwor a suitable twin-screw extruder. An extruder (e.g., single or twinscrew) can be used to provide a pre-foam composition. The extruder canhave a motor to turn a screw inside the extruder. Screw may be a singlescrew or twin screws made of individual elements of various sizes andpitches appropriate for mixing or kneading the specific materials used.In some examples, the extruder has a twin screw.

The various components that make up the pre-foam compositions of thevarious examples described herein (e.g., a polymer comprising styrenerepeating units and non-styrenic repeating units; a C₄-C₁₀₀ unsaturatedolefin; and optionally one or more additional components selected froman ethylene vinyl acetate copolymer; an olefin block copolymer; blowingagent; a crosslinking agent, and any combination thereof) are added intothe extruder through a port. In some examples, the pre-foam compositionsof the various examples described herein can be at least partiallycrosslinked at a first crosslinking temperature in, e.g., section ofextruder to form a crosslinked pre-foam composition (e.g., at leastpartially crosslinked pre-foam composition), which, in some examples,may be a thermoplastic crosslinked pre-foam composition. Various othercomponents (e.g., pigments, fillers, and blowing agents) can be addedvia a port into the extruder and mixed or kneaded with the pre-foamcompositions and/or the crosslinked pre-foam composition (e.g., at leastpartially crosslinked pre-foam composition).

The various components that make up the pre-foam compositions of thevarious examples described herein may be added as a melt or asappropriately-sized solid particles, for example chips or pellets, thatare melted in section as they are mixed or kneaded with, e.g., thecrosslinked pre-foam composition (e.g., at least partially crosslinkedpre-foam composition).

The contents of the extruder or mixer may be heated to, achieve, amongother things, crosslinking of the pre-foam compositions to give acrosslinked pre-foam composition (e.g., at least partially crosslinkedpre-foam composition). In other examples, the heating may triggerfoaming (i.e., blowing) (e.g., via triggering a chemical blowing agent),thereby converting the crosslinked pre-foam composition (e.g., at leastpartially crosslinked pre-foam composition) to a foam composition thatis sufficiently thermoplastic to be extruded or injected into a moldfrom the extruder 10. Alternatively, the crosslinked pre-foamcomposition (e.g., at least partially crosslinked pre-foam composition)can be foamed in the extruder using a physical blowing agent. And, insome examples, a chemical blowing agent can also be present, such that,when there is heating, the heating can trigger the chemical blowingagent.

In some examples, the pre-foam compositions may be added as a melt at atemperature close to or at the crosslinking temperature such thatcrosslinking can occur, but at a temperature that is sufficiently belowthe temperature that would trigger blowing. The temperature of theextruder can then be increased to a temperature close to or at thetriggering temperature of a chemical blowing agent, thereby giving afoam composition.

The extent to which the pre-foam compositions is crosslinked to give acrosslinked pre-foam composition (e.g., at least partially crosslinkedpre-foam composition) can be controlled so that the crosslinked pre-foamcomposition (e.g., at least partially crosslinked pre-foam composition)remains thermoplastic and can be mixed with various other components(e.g., pigments, fillers, and blowing agents) if necessary. This can beaccomplished in various ways, for instance by controlling the amount oftime for crosslinking; by controlling the crosslinking temperature; bycausing a temperature reduction at a desired point of crosslinking tostop or slow further crosslinking; or by a combination of these. Forexample, the amount of time for crosslinking can be controlled bycontrolling screw speed, by locating port 8 closer to or further fromport 6, or by a combination of these.

In some examples, as the crosslinking density increases, the crosslinkedpre-foam composition (e.g., at least partially crosslinked pre-foamcomposition) can form phase separated domains, wherein, for example, thestyrenic segments of the crosslinked polymer comprising styrenerepeating units and non-styrenic repeating units phase separate intopredominately styrene-rich domains.

A crosslinked pre-foam composition (e.g., at least partially crosslinkedpre-foam composition) or a foam composition, each of which issufficiently thermoplastic to be extruded or injected into a mold fromthe extruder, is extruded at an end of the extruded opposite the motor.In some examples, a vacuum port may be used to remove volatiles, forexample water, volatile organic liquids that may have been introduced assolvents with some materials, crosslinking reaction by-products orblowing agent by-products. The extrudate may be shaped by being extrudedthrough a die (not shown). For example, the extrudate (e.g., crosslinkedpre-foam composition or foam composition) may be extruded in the form ofstrands that are then pelletized, in the form of a tube, or in the formof a sheet. The pelletization can be conducted using a cooled die.Additionally or alternatively, the pelletization can be performed underwater, thus cooling the resulting pellets as they exited thepelletization die.

In some examples, the foam preforms of the various examples describedherein are obtained by blowing the pre-foam composition, the crosslinkedcomposition, or both the pre-foam composition and the crosslinkedcomposition by about 150% to about 240% (e.g., from about 150% to about220%; about 150% to about 200%, about 175% to about 225%, about 180% toabout 230% or about 160% to about 240%) in at least one dimension (e.g.,the vertical dimension) using a blowing agent.

In some examples, the foam preforms of the various examples describedherein are made using a process that involves impregnating a pre-foamcomposition, a crosslinked pre-foam composition or combinations thereof(e.g., at or above a softening temperature of the pre-foam composition,crosslinked pre-foam composition or combinations thereof) with aphysical blowing agent at a first concentration or first pressure.

As used herein, the term “impregnating” generally means dissolving orsuspending a physical blowing agent in a pre-foam composition, acrosslinked pre-foam composition or combinations thereof. Theimpregnated pre-foam composition, crosslinked pre-foam composition orcombinations thereof can then be foamed, or can be cooled (whenapplicable) and re-softened (when applicable) for blowing at a latertime.

In some instances, the impregnated pre-foam composition, crosslinkedpre-foam composition or combinations thereof is foamed by reducing theconcentration or pressure of the physical blowing agent. The reductionin concentration of the physical blowing agent can release additionalamounts (e.g., to create a secondary expansion of an originally-formedmicrocell in the pre-foam composition, crosslinked pre-foam compositionor combinations thereof) of the impregnated physical blowing agent fromthe pre-foam composition, crosslinked pre-foam composition orcombinations thereof, to further blow the pre-foam composition,crosslinked pre-foam composition or combinations thereof, forming a foamcomposition (e.g., a foam composition having a closed-cell structure).

In addition to injection molding, the pre-foam compositions of thepresent disclosure can be foamed and optionally molded using variousprocesses known in the art. For example, the pre-foam compositions canbe used to form slab foam, particulate (e.g., bead) foams of variousshapes and sizes, etc. These various forms of foam can then be used indifferent ways. For example, slab foam can be used directly as afinished foam article, can be shaped (e.g., cut or trimmed) to form afinished foam article, or can be compression molded to form a finishedfoam article. The foams can be subjected to annealing processes as partof forming the finished foam article. Pellets of the pre-foamcompositions can be used to form individual particulate foams, or can befoamed and molded to form unitary molded foam articles composed ofindividual portions of foam affixed to each other.

The foam compositions of the various examples described herein (e.g.,foam preforms) may be further shaped or molded by any of the methodsknown for forming articles from thermoplastic materials.

Another step of the method for forming compression molded foam includesproviding a foam preform that has been foamed using any suitable blowingprocess (e.g., blowing using a physical and/or chemical blowing agent),and then compression molding the foam preform to form a compressionmolded foam.

In some examples, the foam preform is prepared by a process comprising(i) softening a pre-foam composition, a crosslinked pre-foam compositionor combinations thereof (e.g., by heating at a first temperature at orabove a softening temperature of the pre-foam composition, crosslinkedpre-foam composition or combinations thereof); (ii) simultaneously orsequentially with the softening (when applicable), contacting thepre-foam composition, crosslinked pre-foam composition or combinationsthereof with a first concentration or first pressure of a physicalblowing agent sufficient to drive an amount of the physical blowingagent into the pre-foam composition, crosslinked pre-foam composition orcombinations thereof; (iii) changing the concentration or pressure(e.g., decreasing the pressure or concentration) of the physical blowingagent to a second concentration or second pressure that is effective tofoam the pre-foam composition, crosslinked pre-foam composition orcombinations thereof, thereby forming a foam composition (e.g., a foamcomposition having a closed-cell structure); and, (iv) following thechanging, cooling (when applicable) the foam composition to (e.g.,cooling to a temperature below the softening temperature of the foamcomposition), to form a foam preform having an initial height. In someexamples, this process is conducted with a composition comprising,consisting essentially of or consisting of a crosslinked pre-foamcomposition.

In other examples, the foam preform is prepared by (i) contacting (e.g.,dissolving or suspending) the pre-foam composition, crosslinked pre-foamcomposition or combinations thereof with a first concentration of achemical blowing agent, in some examples, at or above a softeningtemperature of the pre-foam composition, crosslinked pre-foamcomposition or combinations thereof; (ii) triggering the chemicalblowing agent to foam the pre-foam composition, crosslinked pre-foamcomposition or combinations thereof, thereby forming a foam composition(e.g., a foam composition having a closed-cell structure); and, (iii)following the triggering, in some examples, cooling the foam compositionto, e.g., a temperature below its softening temperature, to form a foampreform having an initial height. In some examples, this process isconducted with a composition comprising, consisting essentially of orconsisting of a crosslinked pre-foam composition. In some examples, the“triggering” of the chemical blowing agent is performed by any suitablemethod, including heating the pre-foam composition, crosslinked pre-foamcomposition or combinations thereof comprising a concentration of thechemical blowing agent to a temperature sufficient to “trigger” thechemical blowing agent, wherein the concentration of the chemicalblowing agent is effective to foam the pre-foam composition, crosslinkedpre-foam composition or combinations thereof, thereby forming a foamcomposition (e.g., a foam composition having a closed-cell structure).

In some examples, the contacting comprises contacting at a pressure offrom about 10 MPa to about 100 MPa (e.g., from about 30 MPa to about 100MPa, about 20 MPa to about 80 MPa, about 30 MPa to about 60 MPa or about40 MPa to about 70 MPa).

In some examples, whether the foam preform is prepared using a physicalor chemical blowing agent, a foamed composition (e.g, in the form of afoam preform) can be compression molded. For example, the foamedcomposition can be compression molded by placing the foam preform in acompression mold having a height less than the initial height of thefoam preform and closing the mold, thereby compressing the foam preformto the height of the mold.

Simultaneously or sequentially with the compressing, the foam preformcan be heated in the closed compression mold. During the compressionmolding, the temperature of at least a portion of the foam preform inthe closed mold can be raised to a temperature within ±30° C. of thesoftening temperature of the foam composition. The temperature can beraised by heating the closed mold. Following the raising of thetemperature, while the foam preform remains closed in the compressionmold, the temperature of at least a portion of the foam preform can belowered. The temperature can be lowered by cooling the closed mold. Thelowering can lower the temperature of at least a portion of the foampreform to a temperature at least 35° C. below the softening temperatureof the foamed composition, thereby forming the compression molded foam.

Following the cooling, the compression mold can be opened, and thecompression molded foam can be removed from the compression mold.

Some examples contemplated herein are directed to compression moldedcomponents of articles of footwear or athletic equipment made inaccordance with the compositions and processes described herein.

Other examples contemplated herein are directed to methods ofmanufacturing articles of footwear or athletic equipment. For example,the method can comprise providing a compression molded foam component ofan article of footwear in accordance with the present disclosure, andcombining the component with a footwear upper and an outsole to form thearticle of footwear. Similarly, the method can comprise providing acompression molded foam component of an article of athletic equipment inaccordance with the present disclosure, and combining the compressionmolded foam component with other components to form a finished articleof athletic equipment.

One method of making a compression molded foam (and compression moldedfoam articles) described herein comprises forming a foam preform andcompression molding the foam preform to make a compression molded foam.In some examples, the foam preforms of the various examples describedherein are obtained by blowing the pre-foam composition, the crosslinkedcomposition, or both the pre-foam composition and the crosslinkedcomposition by about 150% to about 240% (e.g., from about 150% to about220%; about 150% to about 200%, about 175% to about 225%, about 180% toabout 230% or about 160% to about 240%) in at least one dimension (e.g.,the vertical dimension) using a blowing agent. In some examples, theblown pre-foam composition, the crosslinked composition, or both thepre-foam composition and the crosslinked composition can be compressionmolded to about 120% to about 200% (e.g., from about 120% to about 180%;about 130% to about 190%; about 150% to about 200%; or about 160% toabout 190%) in at least one dimension.

Thus for example, if the foaming of the pre-foam composition, thecrosslinked composition, or both the pre-foam composition and thecrosslinked composition is about 200%, the blown pre-foam composition,the crosslinked composition, or both the pre-foam composition and thecrosslinked composition can be compression molded by a net 20% bycompression molding to about 180%. In another example, if the pre-foamcomposition, the crosslinked composition, or both the pre-foamcomposition and the crosslinked composition is blown into a 20 mm(height)×10 cm (width)×5 cm (depth) slab, and the slab is compressionmolded in the height direction by 20%, the compression molded slab wouldhave the dimensions 18 mm (height)×10 cm (width)×5 cm (depth). In someexamples, the compression molding is substantially maintained.

In some examples, the foam preform is made using a process that involvesimpregnating a pre-foam composition, a crosslinked pre-foam compositionor combinations thereof (e.g., at or above a softening temperature ofthe pre-foam composition, crosslinked pre-foam composition orcombinations thereof) with a physical blowing agent at a firstconcentration or first pressure. The impregnated pre-foam composition,crosslinked pre-foam composition or combinations thereof can then befoamed, or can be cooled (when applicable) and re-softened (whenapplicable) for blowing at a later time. In some instances, theimpregnated pre-foam composition, crosslinked pre-foam composition orcombinations thereof is foamed by reducing the concentration or pressureof the physical blowing agent. The reduction in concentration of thephysical blowing agent can release additional amounts of the impregnatedphysical blowing agent from the pre-foam composition, crosslinkedpre-foam composition or combinations thereof, to further blow thepre-foam composition, crosslinked pre-foam composition or combinationsthereof, forming a foam composition (e.g., a foam composition having aclosed-cell structure).

In some examples, the compression molding process is conducted byheating the foam preform in a closed compression mold. The foam preformis heated to a temperature close to its softening temperature, to allowthe foam to retain the shape of the compression mold. For example, thefoam preform can be heated to a temperature within ±30° C. of itssoftening temperature, or within ±20° C. of its softening temperature,or within ±10° C. of its softening temperature, or within ±5° C. of itssoftening temperature. For example, the foam preform can be heated to atemperature of from about 100° C. to about 250° C., or of from about140° C. to about 220° C., or of from about 100° C. to about 150° C., orof from about 130° C. to about 150° C.

The material used to form the compression mold can be any material whichcan withstand the temperatures used during the process, such as machinedmetals, including aluminum. The compression mold can be made using twopieces, such as a top and a bottom mold. Depending on the shape of thefoam component to be molded, a multiple-piece mold may be used in orderto more easily release the compression molded foam from the mold.

The compression molding of the foam preform in the compression mold canresult in a closed skin forming on the final compression molded foamcomponent. However, care should be taken during the compression moldingnot to subject the foam preform to conditions such that more than adesired amount of the closed cell structures of the foam collapse. Oneway to avoid collapsing more than a desired amount of the closed cellstructures is to control the temperature of the polymeric composition,for example, by controlling the temperature of the mold. For example,during the compression molding step, the heating of the foam preform inthe compression mold can be conducted for time of from 100 seconds to1,000 seconds, or of from 150 seconds to 700 seconds.

Once the foam preform has been heated in the compression mold at theappropriate temperature for the desired length of time to soften thepreform to the desired level, the softened preform is cooled, forexample, to a temperature at least 35° C. below its softeningtemperature, or at least 50° C. below its softening temperature, or atleast 80° C. below its softening temperature, to re-solidify thesoftened foam, thereby forming the compression molded foam. Once cooled,the compression molded foam component is removed from the compressionmold. Following the heating, the cooling of the foam preform in thecompression mold can be conducted for a time of from 50 to 1,000seconds, or for a time of from 100 to 400 seconds.

Compositions

In various aspects, compositions are provided that can be foamed, i.e.can be used to form a foam composition. In some aspects, thesecompositions are referred to as a “pre-foam composition.” In someaspects, the compositions can be used to generate foam compositions thatare soft and have a high energy return making them useful for footwear.The compositions can be used to generate foams using any of a variety ofmethods known in the art. In some aspects, the foams are generated usinginjection molding or injection molding followed by compression moldingtechniques. The foamed compositions can include components of articlesof footwear as described above, for example a midsole 146 as depicted inFIGS. 1A-1B.

The compositions described herein, when used to form foams, in someaspects produced foams having surprisingly high energy return/resiliencyvalues. These compositions also, when used to form foams, in someaspects produce foams having high split-tear values. The compositionscan, in some aspects, be used to produce foams having other beneficialproperties, including additional properties beneficial for use infootwear including as cushioning components. The compositions of thepresent disclosure can be foamed and/or molded using various methods. Inone example, the polymeric compositions can be foamed as part of aninjection molding process. Optionally, the injection molded foam cansubsequently be compression molded. Compression molding of the injectionmolded foam can modify the properties of the polymeric foam, such asreducing the compression set of the foam, which can be beneficial forfoams used in footwear-related applications. Foams formed from thepolymeric compositions of the present disclosure can be used infootwear-related applications without being compression molded.

In some aspects, a composition is provided including a block copolymerincluding (1) a first block and a third block, each independentlyincluding a linear or branched chain aliphatic polymer having aplurality of aromatic groups attached pendantly thereto, (2) a secondblock located between the first block and the third block and includingan aliphatic polymer having a plurality of aliphatic side chainsattached thereto, and (3) a plurality of first ethylenically unsaturatedgroups present on one or more of the first block, second block, andthird block. The block copolymer can include about 50% to 95%, about 60%to 90%, or about 60% to 85% of the second blocks by weight based uponthe weight of the block copolymer. The compositions can also include anolefinic copolymer having a plurality of first olefinic segments and aplurality of second olefinic segments having a different chemicalstructure from the first olefinic segments; and one or more linkingpolymers, each linking polymer having one or more third olefinicsegments. The compositions can include an ethylene vinyl acetate (EVA)copolymer.

In certain aspects, it has been observed that the ratios of thematerials in the compositions strongly impact the foam properties suchas energy return, durability, and softness. In some aspects, a sum of aratio I, II, III, IV, and V is from about 1.0 to 10.0, about 1.0 to 8.0,about 1.0 to 5.0, about 1.5 to 5.0, about 1.5 to 8.0, about 3.5 to 8.0,or about 3.5 to 5.0; wherein the ratio I is a ratio of a total parts byweight of the olefinic copolymers present in the composition to a totalparts by weight of the block copolymer present in the composition;wherein the ratio II is a ratio of a total parts by weight of thelinking polymers present in the composition to a total parts by weightof the block copolymer present in the composition; wherein the ratio IIIis ratio of a total parts by weight of the EVA copolymers present in thecomposition to a total parts by weight of the block copolymer present inthe composition; wherein the ratio IV is a ratio of the total parts byweight of the linking polymers present in the composition to a totalparts by weight of the block copolymers present in the composition, andwherein the ratio V is a ratio of the total parts by weight of the oneor more EVA copolymers present in the composition to a total parts byweight of the one or more olefinic copolymers present in thecomposition.

The block copolymer can include (1) a first block and a third block,each independently including a linear or branched chain aliphaticpolymer having a plurality of aromatic groups attached pendantlythereto, (2) a second block located between the first block and thethird block and including an aliphatic polymer having a plurality ofaliphatic side chains attached thereto, and (3) a plurality of firstethylenically unsaturated groups present on one or more of the firstblock, second block, and third block. The aromatic groups can bestyrenic groups. The aliphatic groups can include one or moresubstituted or unsubstituted alkyl side chains having 2 to 20, 2 to 18,2 to 15, 2 to 12, 5 to 12, 5 to 15, 5 to 18, or 5 to 20 carbon atoms.

The olefinic copolymer can have a plurality of first olefinic segmentsand a plurality of second olefinic segments having a different chemicalstructure from the first olefinic segments. For example, the olefinicblock copolymer can be a copolymer of ethylene and the secondalpha-olefin. In some aspects, the second alpha-olefin has 4 to 20, 4 to18, 4 to 15, 4 to 12, 6 to 12, 6 to 15, 6 to 18, or 6 to 20 carbonatoms. The olefinic block copolymer can have one or more blocks rich inthe first alpha-olefin and one or more blocks rich in the secondalpha-olefin.

The linking polymers can each, independently, have one or more thirdolefinic segments. In some aspects, the compositions include a firstalpha-olefin linking polymer and a second alpha-olefin linking polymerdifferent from the first alpha-olefin linking polymer. For example, thefirst alpha-olefin linking polymer and the second alpha-olefin linkingpolymer can both be copolymers of ethylene and 1-butene, each having adifferent ratio of ethylene to 1-butene monomer content in thecopolymer.

The ethylene vinyl acetate (EVA) copolymer can have a vinyl acetatecontent of about 5% to 50%, about 5% to 45%, about 5% to 40%, about 10%to 50%, about 10% to 45%, about 10% to 40%, about 15% to 40%, about 15%to 45%, about 15% to 50%, about 20% to 50%, or about 30% to 50% byweight based upon the weight of the ethylene-vinyl acetate copolymer.

In some aspects, a composition is provided including a block copolymerhaving a first block and a third block, each independently comprising alinear or branched chain aliphatic polymer having a plurality ofaromatic groups attached pendantly thereto, a second block locatedbetween the first block and the third block and comprising an aliphaticpolymer having a plurality of aliphatic side chains attached thereto,and a plurality of first ethylenically unsaturated group present on oneor more of the first block, second block, and third block; wherein theblock copolymer contains about 40% to 95%, about 40% to 90%, about 50%to 90%, about 60% to 90%, or about 65% to 85% of the second blocks byweight based upon the weight of the block copolymer; an olefiniccopolymer comprising a plurality of first olefinic segments and aplurality of second olefinic segments having a different chemicalstructure from the first olefinic segments; one or more linkingpolymers, each linking polymer comprising one or more third olefinicsegments; and an ethylene vinly-acetate copolymer.

In some aspects, a composition is provided including an A-B-A blockcopolymer, wherein each of the A blocks comprise styrenic repeat units,the B block is a random copolymer of ethylene and an alpha-olefin having2 to 12, 2 to 10, 2 to 8, 3 to 8, 3 to 10, 3 to 12, 6 to 12, or 6 to 8carbon atoms, and wherein the A-B-A-block copolymer comprises about 5%to 50%, about 10% to 50%, about 10% to 40%, or about 15% to 35% of the Ablocks by weight based upon the weight of the A-B-A block copolymer; anolefinic block copolymer, wherein the olefinic block copolymer is acopolymer of ethylene and an alpha-olefin having 2 to 12, 2 to 10, 2 to8, 3 to 8, 3 to 10, 3 to 12, 6 to 12, or 6 to 8 carbon atoms, andwherein the olefinic block copolymer has one or more blocks rich in theethylene and one or more blocks rich in the alpha-olefin; analpha-olefin linking polymer, wherein the alpha-olefin linking polymeris a copolymer of ethylene and an alpha-olefin having about 2 to 12, 2to 10, 2 to 8, 3 to 8, 3 to 10, 3 to 12, 6 to 12, or 6 to 8 carbonatoms, and wherein the alpha-olefin linking polymer has an alpha-olefinmonomer content of about 15% to about 40% by weight based upon theweight of the alpha-olefin linking polymer; and an ethylene-vinylacetate copolymer having a vinyl acetate content of about 5% to 50%,about 5% to 45%, about 5% to 40%, about 10% to 50%, about 10% to 45%,about 10% to 40%, about 15% to 40%, about 15% to 45%, about 15% to 50%,about 20% to 50%, or about 30% to 50% by weight based upon the weight ofthe ethylene-vinyl acetate copolymer.

In some aspects, each of the A blocks consists essentially ofpolystyrene. In some aspects, the B block consists essentially of acopolymer of ethylene and octene. In some aspects, the B block consistsessentially of a copolymer of ethylene and butadiene.

In some aspects, a composition is provided including a partiallyhydrogenated thermoplastic elastomeric block copolymer, the partiallyhydrogenated thermoplastic elastomeric block copolymer comprising one ormore A blocks comprising aromatic repeat units, one or more B blockscomprising aliphatic repeat units, and one or more first ethylenicallyunsaturated groups present on one or both of the aromatic repeat unitsand the aliphatic repeat units; an olefinic block copolymer, wherein theolefinic block copolymer is a copolymer of a first alpha-olefin and asecond alpha-olefin different from the first alpha-olefin, and whereinthe olefinic block copolymer comprising one or more second ethylenicallyunsaturated groups; an alpha-olefin linking polymer, wherein thealpha-olefin linking polymer comprises one or more aliphatic sidechains;and an ethylene-vinyl acetate copolymer; wherein a sum of a ratio I, II,III, IV, and V is from about 1.0 to 10.0, about 1.0 to 8.0, about 1.0 to5.0, about 1.5 to 5.0, about 1.5 to 8.0, about 3.5 to 8.0, or about 3.5to 5.0. The ratio I is a ratio of a total parts by weight of theolefinic copolymers present in the composition to a total parts byweight of the partially hydrogenated thermoplastic elastomeric blockcopolymer present in the composition. The ratio II is a ratio of a totalparts by weight of the alpha-olefin linking polymers present in thecomposition to a total parts by weight of the partially hydrogenatedthermoplastic elastomeric block copolymer present in the composition.Ratio III is ratio of a total parts by weight of the ethylene-vinylacetate copolymers present in the composition to a total parts by weightof the partially hydrogenated thermoplastic elastomeric block copolymerpresent in the composition. Ratio IV is a ratio of the total parts byweight of the alpha-olefin linking polymers present in the compositionto a total parts by weight of the partially hydrogenated thermoplasticelastomeric block copolymer present in the composition. Ratio V is aratio of the total parts by weight of the one or more ethylene-vinylacetate copolymers present in the composition to a total parts by weightof the one or more olefinic copolymers present in the composition.

In some aspects, a composition is provided including a partiallyhydrogenated thermoplastic elastomeric block copolymer, the partiallyhydrogenated thermoplastic elastomeric block copolymer including one ormore A blocks comprising aromatic repeat units, one or more B blockscomprising aliphatic repeat units, and one or more first ethylenicallyunsaturated groups present on one or both of the aromatic repeat unitsand the aliphatic repeat units; an olefinic block copolymer, wherein theolefinic block copolymer is a copolymer of a first alpha-olefin and asecond alpha-olefin different from the first alpha-olefin, and whereinthe olefinic block copolymer comprising one or more second ethylenicallyunsaturated groups; an alpha-olefin linking polymer, wherein thealpha-olefin linking polymer comprises one or more aliphatic sidechains;and an ethylene-vinyl acetate copolymer.

In some aspects, a composition is provided including one or morepartially hydrogenated thermoplastic elastomeric block copolymers, eachof the one or more partially hydrogenated thermoplastic elastomericblock copolymers independently comprising one or more aromatic blocks,one or more aliphatic blocks, and one or more first ethylenicallyunsaturated units; one or more olefinic block copolymers, each of theone or more olefinic block copolymers comprising second ethylenicallyunsaturated units; one or more alpha-olefin linking polymers; and one ormore ethylene-vinyl acetate copolymers; wherein a sum of a ratio I, II,III, IV, and V is from about 1.0 to 10.0, about 1.0 to 8.0, about 1.0 to5.0, about 1.5 to 5.0, about 1.5 to 8.0, about 3.5 to 8.0, or about 3.5to 5.0. Ratio I is a ratio of a total parts by weight of the olefinicblock copolymers present in the composition to a total parts by weightof the partially hydrogenated thermoplastic elastomeric block copolymerpresent in the composition. Ratio II is a ratio of a total parts byweight of the alpha-olefin linking polymers present in the compositionto a total parts by weight of the partially hydrogenated thermoplasticelastomeric block copolymer present in the composition. Ratio III isratio of a total parts by weight of the ethylene-vinyl acetatecopolymers present in the composition to a total parts by weight of thepartially hydrogenated thermoplastic elastomeric block copolymer presentin the composition. Ratio IV is a ratio of the total parts by weight ofthe alpha-olefin linking polymers present in the composition to a totalparts by weight of the partially hydrogenated thermoplastic elastomericblock copolymer present in the composition. Ratio V is a ratio of thetotal parts by weight of the one or more ethylene-vinyl acetatecopolymers present in the composition to a total parts by weight of theone or more olefinic copolymers present in the composition.

In some aspects, a composition is provided including one or morepartially hydrogenated thermoplastic elastomeric block copolymers, eachof the one or more partially hydrogenated thermoplastic elastomericblock copolymers independently comprising one or more aromatic blocks,one or more aliphatic blocks, and one or more first ethylenicallyunsaturated units; one or more olefinic block copolymers, each of theone or more olefinic block copolymers comprising second ethylenicallyunsaturated units; one or more alpha-olefin linking copolymers; and oneor more ethylene-vinyl acetate copolymers. The partially hydrogenatedthermoplastic elastomeric block copolymer can have an A-B blockstructure or an A-B-A block structure, wherein each of the A blockscomprise one or more aromatic repeat units, and wherein the B block isan aliphatic polymer block comprising the one or more firstethylenically unsaturated units. The partially hydrogenatedthermoplastic elastomeric block copolymer can include about 5% to 50%,about 5% to 40%, about 10% to 50%, about 10% to 40%, about 15% to 40%,or about 15% to 35% of the A block by weight based upon the weight ofthe partially hydrogenated thermoplastic elastomeric block copolymer.

The composition can include about 5 parts by weight to about 30 parts byweight, about 5 parts by weight to about 20 parts by weight, about 5parts by weight to about 15 parts by weight, about 10 parts by weight toabout 20 parts by weight, about 10 parts by weight to about 30 parts byweight, or about 15 parts by weight to about 25 parts by weight of theA-B-A block copolymer or partially hydrogenated thermoplasticelastomeric block copolymer based upon the total weight of thecomposition.

The composition can include about 5 parts by weight to about 15 parts byweight, about 5 parts by weight to about 10 parts by weight, about 10parts by weight to about 15 parts by weight, or about 5 parts by weightto about 20 parts by weight of the A-B-A block copolymer or partiallyhydrogenated thermoplastic elastomeric block copolymer based upon thetotal weight of the composition.

The composition can include about 5 parts by weight to about 20 parts byweight, about 5 parts by weight to about 15 parts by weight, about 10parts by weight to about 20 parts by weight, about 10 parts by weight toabout 15 parts by weight, about 5 parts by weight to about 10 parts byweight, about 15 parts by weight to about 20 parts by weight, about 5parts by weight to about 30 parts by weight, about 5 parts by weight toabout 20 parts by weight, about 5 parts by weight to about 15 parts byweight, about 10 parts by weight to about 20 parts by weight, about 10parts by weight to about 30 parts by weight, or about 15 parts by weightto about 25 parts by weight of the olefinic block copolymer by weightbased upon the total weight of the composition.

The composition can include about 10 parts by weight to about 50 partsby weight, about 15 parts by weight to about 50 parts by weight, about10 parts by weight to about 35 parts by weight, about 10 parts by weightto about 20 parts by weight, about 20 parts by weight to about 30 partsby weight, about 30 parts by weight to about 40 parts by weight, about40 parts by weight to about 50 parts by weight, about 20 parts by weightto about 35 parts by weight, or about 20 parts by weight to about 30parts by weight of the alpha-olefin linking polymer based upon the totalweight of the composition.

The composition can include about 10 parts by weight to about 50 partsby weight, about 10 parts by weight to about 45 parts by weight, about20 parts by weight to about 45 parts by weight, about 20 parts by weightto about 50 parts by weight, about 20 parts by weight to about 30 partsby weight, about 30 parts by weight to about 40 parts by weight, orabout 40 parts by weight to about 50 parts by weight of theethylene-vinyl acetate copolymer based upon the total weight of thecomposition.

In some aspects, a composition is provided including an A-B-A blockcopolymer, wherein each of the A blocks have styrenic repeat units, theB block is a random copolymer of ethylene and a first alpha-olefinhaving 3 to 8 carbon atoms (e.g. 3, 4, 5, 6, 7, or 8 carbon atoms), andwherein the A-B-A-block copolymer includes about 10% to 50%, about 10%to 40%, about 15% to 40%, or about 15% to 30% of the A blocks by weightbased upon an entire weight of the A-B-A block copolymer; an olefinicblock copolymer, wherein the olefinic block copolymer is a copolymer ofethylene and a second alpha-olefin having about 4 to 14, about 6 to 12,or about 6 to 10 carbon atoms, and wherein the olefinic block copolymerhas one or more blocks rich in the ethylene and one or more blocks richin the second alpha-olefin; and an alpha-olefin linking polymer, whereinthe alpha-olefin linking polymer is a copolymer of ethylene and a thirdalpha-olefin having about 2 to 24, about 3 to 24, about 3 to 18, orabout 6 to 18 carbon atoms, and wherein the alpha-olefin linking polymerhas an alpha-olefin monomer content of about 10% to 50%, about 10% to40%, about 15% to 40%, or about 15% to 30% by weight based upon anentire weight of the alpha-olefin linking polymer.

In some aspects, a composition is provided including an A-B-A blockcopolymer, wherein each of the A blocks include repeat units accordingto the following formula

where each occurrence of R¹ is independently a hydrogen, halogen,hydroxyl, or a substituted or unsubstituted alkyl group having from 1 to18, 1 to 15, 1 to 12, 3 to 18, 3 to 15, or 3 to 12 carbon atoms; whereeach occurrence of R² is independently none or a substituted orunsubstituted alkyl group having from 1 to 15, 1 to 12, 1 to 8, 3 to 8,3 to 12, or 3 to 15 carbon atoms; wherein the B block is a randomcopolymer of ethylene and a first alpha-olefin having about 3 to 12, 3to 10, or 3 to 8 carbon atoms; and wherein the A-B-A-block copolymerincludes about 10% to 50%, about 10% to 40%, about 15% to 40%, or about15% to 30% of the A blocks by weight based upon an entire weight of theA-B-A block copolymer; an olefinic block copolymer, wherein the olefinicblock copolymer is a copolymer of ethylene and a second alpha-olefinhaving about 4 to 14, about 6 to 12, or about 6 to 10 carbon atoms, andwherein the olefinic block copolymer has one or more blocks rich in theethylene and one or more blocks rich in the second alpha-olefin; and analpha-olefin linking polymer, wherein the alpha-olefin linking polymeris a copolymer of ethylene and a third alpha-olefin having bout 2 to 24,about 3 to 24, about 3 to 18, or about 6 to 18 carbon atoms; wherein aratio II of a total parts by weight of the A-B-A block copolymer presentin the composition to a total parts by weight of the linking polymerpresent in the is from about 1.00 to 5.00, about 1.00 to 4.00, about1.50 to 4.00, about 1.50 to 3.50, about 1.00 to 3.00, or about 2.00 to4.00.

In some aspects, a composition is provided including an A-B-A blockcopolymer, wherein each of the A blocks include repeat units accordingto the following formula

where each occurrence of R¹ is independently a hydrogen, halogen,hydroxyl, or a substituted or unsubstituted alkyl group having from 1 to18, 1 to 15, 1 to 12, 3 to 18, 3 to 15, 3 to 12, 1 to 8, 3 to 8, 1 to 5,or 3 to 5 carbon atoms; where each occurrence of R² is independentlynone or a substituted or unsubstituted alkyl group having from 1 to 15,1 to 12, 1 to 8, 3 to 8, 3 to 12, 3 to 15, 1 to 8, 1 to 5, or 1 to 3carbon atoms; wherein the B block is a random copolymer of ethylene anda first alpha-olefin having about 3 to 12, 3 to 10, or 3 to 8 carbonatoms; and wherein the A-B-A-block copolymer includes about 10% to 50%,about 10% to 40%, about 15% to 40%, or about 15% to 30% of the A blocksby weight based upon an entire weight of the A-B-A block copolymer; anolefinic block copolymer, wherein the olefinic block copolymer is acopolymer of ethylene and a second alpha-olefin having about 4 to 14,about 6 to 12, or about 6 to 10 carbon atoms, and wherein the olefinicblock copolymer has one or more blocks rich in the ethylene and one ormore blocks rich in the second alpha-olefin; and an alpha-olefin linkingpolymer, wherein the alpha-olefin linking polymer is a copolymer ofethylene and a third alpha-olefin having bout 2 to 24, about 3 to 24,about 3 to 18, or about 6 to 18 carbon atoms.

In some aspects, the alpha-olefin linking polymer has an alpha-olefinmonomer content of about 10% to 50%, about 10% to 45%, about 15% to 45%,about 15% to 40%, or about 20% to 40% by weight based upon an entireweight of the alpha-olefin linking polymer.

In some aspects, each of the A blocks include a large amount ofpolystyrene. For example, each of the A blocks can include at least 80%,90% or more styrene repeat units based upon the number of repeat unitsin the A block. In some aspects, each of the A blocks consistsessentially of polystyrene.

In some aspects, each of the B blocks includes a random copolymer ofethylene and a first alpha-olefin having 4, 5, 6, 7, or 8 carbon atoms.In some aspects, the B block is essentially a random copolymer ofethylene and octene, or is random copolymer of ethylene and butadiene.

In some aspects there can be more than one alpha-olefin linking polymerpresent in the composition. For example, in some aspects, thecomposition includes a first alpha-olefin linking polymer and a secondalpha-olefin linking polymer, wherein the first alpha-olefin linkingpolymer and the second alpha-olefin linking polymer are copolymers ofethylene and 1-butene, each having a different ratio of ethylene to1-butene monomer content in the copolymer.

In some aspects, the composition includes about 5 parts by weight toabout 15 parts by weight of the A-B-A block copolymer, about 10 parts byweight to about 20 parts by weight of the olefinic block copolymer, andabout 25 parts by weight to about 35 parts by weight of the alpha-olefinlinking polymers based upon an entire weight of the composition.

In some aspects, the composition includes an ethylene-vinyl acetatecopolymer having a vinyl acetate content of about 10% to about 45% byweight based upon the weight of the ethylene-vinyl acetate copolymer.

In various aspects, the composition also includes comprising anethylene-vinyl acetate copolymer having a vinyl acetate content of about5% to 55%, about 5% to 50%, about 10% to 50%, about 10% to 45%, or about15% to 40% by weight based upon the weight of the ethylene-vinyl acetatecopolymer. The

The A-B-A block copolymer can be at least partially or fullyhydrogenated. In some aspects, the A-B-A block copolymer has a degree ofhydrogenation of about 40% to 99%, about 50% to 99%, about 50% to 95%,about 50% to 90%, about 50% to 80%, or about 60% to 80%.

In some aspects, a composition is provided including partiallyhydrogenated thermoplastic elastomeric block copolymer, an olefinicblock copolymer, and an alpha-olefin linking polymer. The partiallyhydrogenated thermoplastic elastomeric block copolymer can include oneor more A blocks with aromatic repeat units, one or more B blocks withaliphatic repeat units, and one or more first ethylenically unsaturatedgroups present on one or both of the aromatic repeat units and thealiphatic repeat units. In some aspects, the aromatic repeat units arestyrenic repeat units. The olefinic block copolymer can be a copolymerof a first alpha-olefin and a second alpha-olefin different from thefirst alpha-olefin, and wherein the olefinic block copolymer includesone or more second ethylenically unsaturated groups. The alpha-olefinlinking polymer can include one or more aliphatic sidechains.

In some aspects, the partially hydrogenated thermoplastic elastomericblock copolymer can have an A-B block structure or an A-B-A blockstructure, wherein the A blocks and B blocks are as described herein.For example, each of the A blocks can independently include one or morearomatic repeat units such as styrene. Each of the B blocks can be analiphatic polymer block comprising the one or more first ethylenicallyunsaturated units.

The aromatic repeat units can include any of a variety of aromaticunits. The aromatic repeat units can include aliphatic backbones havinga plurality of aromatic side chains.

In some aspects, a composition is provided including at least onepolymer containing styrenic repeating units and non-styrenic repeatingunits; and at least one C₄-C₁₀₀ unsaturated olefin. The styrenic repeatunits can include blocks of polystyrene. The polymer containing styrenicrepeating units and non-styrenic repeating units can be a blockcopolymer including blocks of polystyrene and non-styrenic polymericblocks. In some examples, the polymer can include non-styrenic repeatingunits selected from the group polyester, poly-C₂-C₈-alkylene units,polyether units, polycarbonate units, polyamide units, polyketone units,polysiloxane units, and any combination thereof. The styrene repeatingunits and non-styrenic repeating units (e.g., polyester,poly-C₂-C₈-alkylene units, polyether units, polycarbonate units,polyamide units, polyketone units, polysiloxane units, and anycombination thereof), can be in any order. Mixtures of two or morepolymers including styrenic repeat units and non-styrenic repeat unitsare also contemplated herein.

As used herein, unless otherwise dictated by context, when two of thesame type of components are said to be “different” this means that onehas a different chemical composition from the other. For example, thesecond alpha-olefin being different from the first alpha-olefin meansthe second alpha-olefin has a chemical formula that is different fromthe chemical formula of the first alpha-olefin.

In some specific examples, the compositions include a polymer includingstyrene repeating units and non-styrenic repeating units, wherein thepolymer includes block units of polyester. In some examples, the polymerincluding styrenic repeating units and non-styrenic repeating unitsincludes poly-C₂-C₈-alkylene units. In some examples, the polymerincluding styrenic repeating units and non-styrenic repeating units ofthe various examples described herein includes units of polyethylene. Insome examples, the polymer including styrenic repeating units andnon-styrenic repeating units of the various examples described hereinincludes units of polypropylene. In other examples, the polymerincluding styrenic repeating units and non-styrenic repeating units ofthe various examples described herein includes units of polybutylene. Instill other examples, the polymer including styrene repeating units andnon-styrenic repeating units of the various examples described hereinincludes units of polybutadiene. In yet other examples, the polymerincluding styrenic repeating units and non-styrenic repeating units ofthe various examples described herein includes units of polyisoprene.The non-styrenic repeating units of the polymer can includepolyethylene, polypropylene, polybutylene, polybutadiene, polyisoprene,or any combination thereof, and can be present in the polymer in anyorder.

In some examples, when the polymer comprising styrene repeating unitsand non-styrenic repeating units described herein comprise polyethylene,the polyethylene content of the polymer comprising styrene repeatingunits and non-styrenic repeating units is from about 50 mol % to about80 mol % (e.g., from about 50 mol % to about 75 mol %; about 60 mol % toabout 80 mol %; about 55 mol % to about 70 mol %; about 65 mol % toabout 80 mol %; or about 70 mol % to about 80 mol %).

In some examples the polymer comprising styrene repeating units andnon-styrenic repeating units is a PS_(q)-X¹ _(n)-X² _(m)-X³ _(p) blockcopolymer wherein: PS represents polystyrene; X¹ is apoly-C₂-C₈-alkylene; X² is a poly-C₂-C₈-alkylene; X³ is polyether,polyester, polycarbonate, polyamide, polyketone or polysiloxane; thesubscripts q, n, m, and p represent mole fractions; 1>q>0, n is 0 to 1,m is 0 to 1, and p is 0 to 1, provided that q+n+m+p=1; and the order ofthe PS, X¹, X², and X³ blocks can be random or in the order shown. Insome examples, X¹ is polyethylene, polypropylene, polybutylene,polybutadiene, or polyisoprene. In other examples, X² is polyethylene,polypropylene, polybutylene, polybutadiene, or polyisoprene.

Some examples of polymers comprising styrene repeating units andnon-styrenic repeating units contemplated herein includestyrene-butadiene-styrene block copolymers; styrene-polybutylene-styreneblock copolymers; styrene-ethylene-butadiene-styrene block copolymers;styrene-ethylene-polybutylene-styrene block copolymers;styrene-isoprene-butadiene-styrene block copolymers; and combinationsthereof.

Generally speaking, the block copolymers, such as the A-B-A blockcopolymer or the polymer comprising styrene repeating units andnon-styrenic repeating units described herein, can be at least partiallyunsaturated (e.g., comprising ethylenic unsaturation). Thus, forexample, at least one of the repeating units can comprise ethylenicunsaturation. As used herein, the term “partially unsaturated” (e.g.,comprising ethylenic unsaturation) generally means that the polymer canhave from about 20 mol % to about 60 mol % unsaturation (e.g., fromabout 20 mol % to about 50 mol %, about 20 mol % to about 30 mol %;about 25 mol % to about 45 mol %; about 30 mol % to about 50 mol %;about 20 mol % to about 40 mol %; or about 25 mol % to about 40 mol %unsaturation, such as ethylenic unsaturation). But it should beunderstood that, by virtue of the fact that polymers comprising styrenerepeating units comprise phenyl rings, they will be “partiallyunsaturated.”

Generally speaking, partial unsaturation makes it possible to formcovalent crosslinking between, for example, the polymer comprisingstyrene repeating units and non-styrenic repeating units (intermolecularand intramolecular); the C₄-C₁₀₀ unsaturated olefin (intermolecular andintramolecular); and between the polymer comprising styrene repeatingunits and non-styrenic repeating units and the C₄-C₁₀₀ unsaturatedolefin.

Generally speaking, the block copolymers, such as the A-B-A blockcopolymer or the polymer comprising styrene repeating units andnon-styrenic repeating units described herein, have a weight averagemolecular weight (Mw) from about 25,000 g/mol to about 1.5×10⁶ g/mol(e.g., from about 250,000 g/mol to about 1.5×10⁶ g/mol, about 25,000g/mol to about 100,000 g/mol; about 50,000 g/mol to about 200,000 g/mol,75,000 g/mol to about 150,000 g/mol; about 100,000 g/mol to about300,000 g/mol; about 250,000 g/mol to about 750,000 g/mol; about 300,000g/mol to about 800,000 g/mol; about 250,000 g/mol to about 650,000g/mol; about 500,000 g/mol to about 1.5×10⁶ g/mol; about 750,000 g/molto about 1.5×10⁶ g/mol; or about 650,000 g/mol to about 1.3×10⁶ g/mol).

Some examples of polymers comprising styrene repeating units andnon-styrenic repeating units include those available from KratonPerformance Polymers Inc., Houston, Tex., such as KRATON® Dstyrene-butadiene-styrene (SBS) polymer comprising styrene repeatingunits and non-styrenic repeating units; KRATON® Dstyrene-isoprene-styrene/styrene-isoprene-butadiene-styrene polymercomprising styrene repeating units and non-styrenic repeating units(SIS)/(SIBS); KRATON® Gstyrene-ethyelen-butadiene-styrene/styrene-ethylene-propylene-styrene(SEBS/SEPS) polymer comprising styrene repeating units and non-styrenicrepeating units; and KRATON® FG maleic anhydride-graftedstyrene-ethyelen-butadiene-styrene (SEBS) polymer comprising styrenerepeating units and non-styrenic repeating units. Some examples ofpolymer comprising styrene repeating units and non-styrenic repeatingunits also include SEPTON® hydrogenated polymer comprising styrenerepeating units and non-styrenic repeating units (e.g., SEPTON® 4055;SEPTON® 8006; SEPTON® 4077; and SEPTON® 4099) available from KurarayCo., Ltd., Tokyo, Japan. Other examples of polymer comprising styrenerepeating units and non-styrenic repeating units include hydrogenatedSEBS block copolymers available from Asahi Kasei Chemicals Corporation(e.g., the various grades of TUFTEC® hydrogenated SEBS block copolymers,including TUFTEC® P1083). While not being bound by any specific theory,it is believed that the level of hydrogenation of the polymer comprisingstyrene repeating units and non-styrenic repeating units, which in someexamples influences (e.g., reduces) the level of ethylenic unsaturationof the polymer comprising styrene repeating units and non-styrenicrepeating units, can influence the crystallinity and/or rigidity of thepolymer comprising styrene repeating units and non-styrenic repeatingunits. Thus, for example, partially hydrogenated polymer comprisingstyrene repeating units and non-styrenic repeating units (e.g., thosethat are about 50 to about 80% hydrogenated) can be less crystalline andmore rigid than their non-hydrogenated counterparts (e.g., those thatare less than about 50% hydrogenated).

In one aspect, the pre-foam compositions of the various examplesdescribed herein can comprise any suitable amount of a polymercomprising styrene repeating units and non-styrenic repeating units. Insome examples, the pre-foam compositions comprise from about 5 wt. % toabout 50 wt. % (e.g., from about 5 wt. % to about 20 wt. %; about 15 wt.% to about 40 wt. %; about 10 wt. % to about 45 wt. %; about 25 wt. % toabout 50 wt. %; or about 20 wt. % to about 45 wt. %) of the polymercomprising styrene repeating units and non-styrenic repeating units. Inaddition, or alternatively, the polymer comprising styrene repeatingunits and non-styrenic repeating units comprises a content of styrenerepeating units from about 5 mol % to about 50 mol % (e.g., from about 5mol % to about 20 mol %; about 15 mol % to about 40 mol %; about 10 mol% to about 45 mol %; about 25 mol % to about 50 mol %; or about 20 mol %to about 45 mol %). In addition, or alternatively, the polymercomprising styrene repeating units and non-styrenic repeating unitscomprises a content of non-styrenic repeating units from about 50 mol %to about 95 mol % (e.g., from about 50 mol % to about 80 mol %, about 60mol % to about 90 mol %, about 70 mol % to about 95 mol % or about 75mol % to about 95 mol %). In some instances, the sum of the content ofstyrene repeating units and the content of non-styrenic repeating unitsis 100 mol %.

In particular examples, the pre-foam compositions described hereincomprise from about 5 parts per hundred of resin (phr) to about 45 phrof the polymer comprising styrene repeating units and non-styrenicrepeating units component (i.e., the styrenic copolymer component). Thepre-foam compositions can comprise from about 10 phr to about 40 phr ofthe styrenic copolymer component. The pre-foam compositions can comprisefrom about 12 phr to about 35 phr of the styrenic copolymer component.The pre-foam compositions can comprise from about 15 phr to about 35 phrof the styrenic copolymer component. The pre-foam compositions cancomprise from about 10 phr to about 30 phr of the styrenic copolymercomponent. The pre-foam compositions can comprise from about 10 phr toabout 25 phr of the styrenic copolymer component. The pre-foamcompositions can comprise from about 10 phr to about 22 phr of thestyrenic copolymer component.

As used herein, the stryrenic copolymer component is understood to referto all the polymers present in the pre-foam composition whichindividually have both styrene repeating units and non-styrenicrepeating units. Thus, the concentration of the styrenic copolymercomponent in a pre-foam composition refers to the total concentration ofeach polymer comprising styrene repeating units and non-styrenicrepeating units present in the composition. In some pre-foamcompositions, the styrenic copolymer component can be formed of only asingle polymer comprising styrene repeating units and non-styrenicrepeating units. In other pre-foam compositions, the styrenic copolymercomponent can be by formed of a plurality of polymers each of which hasboth styrene repeating units and non-styrenic repeating units.

The pre-foam composition described herein also comprises at least oneC₄-C₁₀₀ unsaturated olefin. The C₄-C₁₀₀ unsaturated olefin can be aC₈-C₅₀-unsaturated olefin. The C₄-C₁₀₀ unsaturated olefin can be aC₁₂-C₃₀-unsaturated olefin. The C₄-C₁₀₀ unsaturated olefin can be aC₁₆-C₁₀₀-unsaturated olefin. The C₄-C₁₀₀ unsaturated olefin can be aC₅₀-C₁₀₀-unsaturated olefin. As used herein, the C_(x)-C_(y)nomenclature is understood to specify the carbon length of theunsaturated olefin, not the location of unsaturation. Mixtures of two ormore C₄-C₁₀₀ unsaturated olefins are also contemplated herein. In someexamples, a C₄-C₁₀₀ unsaturated olefin can be pre-polymer (e.g., amonomer); a linear oligomer; a polymer.

As used herein, the term “unsaturated olefin” is understood to encompassany C₄-C₁₀₀ olefin comprising at least one terminal C—C double bond anda total of about 4 to about 100 (e.g., 8 to 50; 12 to 30; 4 to 20; 10 to50; 30 to 90; 20 to 100; 50 to 75; or 20 to 80) total carbon atoms.Additional carbon-carbon double bonds can be present in the unsaturatedolefin. Examples of C₄-C₁₀₀ unsaturated olefins include propene,1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, and 1-octadecene. In other examples,C₄-C₁₀₀ unsaturated olefins can be alkyl- or cycloalkyl-substitutedunsaturated olefins. As used herein, the term “unsaturated olefin” isalso understood to encompass any C₄-C₁₀₀ olefin comprising a pluralityof polymerized units, wherein at least a portion of the polymerizedunits include at least one terminal C—C double bond and a total of about4 to about 100 (e.g., 8 to 50; 12 to 30; 4 to 20; 10 to 50; 30 to 90; 20to 100; 50 to 75; or 20 to 80) total carbon atoms. In other words, theunsaturated olefin can be an unsaturated olefin polymer or copolymer,including unsaturated olefin block copolymers. Additional carbon-carbondouble bonds can be present in the unsaturated olefin polymer orcopolymer. Examples of unsaturated olefinic copolymers include theTAFMER® unsaturated olefin copolymers available from Mitsui ChemicalsAmerica, Inc., Rye Brook, N.Y. (e.g., TAFMER® DF110 and TAFMER® DF605ethylene/unsaturated olefin copolymers); and ENGAGE® and INFUSE® olefinblock copolymers, both available from The Dow Chemical Company, Midland,Mich. (e.g., INFUSE® 9107 olefin block copolymer).

In some examples, the pre-foam compositions of the various examplesdescribed herein can comprise one or more polymers comprising styrenerepeating units and non-styrenic repeating units, one or more C₄-C₁₀₀unsaturated olefins, and one or more olefin block copolymers.

In some examples, C₄-C₁₀₀ unsaturated olefins can comprise one or moreheteroatoms (e.g., —O—, NR¹—, —S(O)_(q)— (wherein q is an integer from 0to 2) and combinations thereof). An example of suchheteroatom-interrupted C₄-C₁₀₀ unsaturated olefins include allyl etherand allyl-terminated polyethylene glycol.

In particular examples, the pre-foam compositions described hereincomprise from about 30 phr to about 90 phr of the C₄-C₁₀₀ unsaturatedolefin component (i.e., the unsaturated olefin component). The pre-foamcompositions can comprise from about 35 phr to about 85 phr of theunsaturated olefin component. The pre-foam compositions can comprisefrom about 40 phr to about 80 phr of the unsaturated olefin component.The pre-foam compositions can comprise from about 45 phr to about 75 phrof the unsaturated olefin component. The pre-foam compositions cancomprise from about 40 phr to about 85 phr of the unsaturated olefincomponent. The pre-foam compositions can comprise from about 45 phr toabout 85 phr of the unsaturated olefin component. The pre-foamcompositions can comprise from about 43 phr to about 82 phr of theunsaturated olefin component.

As used herein, the unsaturated olefin component is understood to referto all the C₄-C₁₀₀ unsaturated olefins present in the pre-foamcomposition. Thus, the concentration of the unsaturated olefin componentin a pre-foam composition refers to the total concentration of eachC₄-C₁₀₀ unsaturated olefin present in the composition, including allC₄-C₁₀₀ unsaturated olefin monomers, C₄-C₁₀₀ unsaturated olefinoligomers, C₄-C₁₀₀ unsaturated olefin polymers, and C₄-C₁₀₀ unsaturatedolefin copolymers. In some pre-foam compositions, the unsaturated olefincomponent can be formed of only a single C₄-C₁₀₀ unsaturated olefin,such as, for example, a single C₄-C₁₀₀ unsaturated olefin copolymer. Inother pre-foam compositions, the unsaturated olefin component can beformed of a plurality of C₄-C₁₀₀ unsaturated olefin, such as, forexample, a plurality of C₄-C₁₀₀ unsaturated olefin copolymers.

The compositions of the various examples described herein can alsocomprise at least one ethylene vinyl acetate copolymer, in addition tothe polymer comprising styrene repeating units and non-styrenicrepeating units; and the C₄-C₁₀₀ unsaturated olefin. And, in someinstances, the at least one ethylene vinyl acetate copolymer comprisestwo different ethylene vinyl acetate copolymers.

In some examples, the at least one ethylene vinyl acetate copolymer is arandom copolymer. In other examples, the at least one ethylene vinylacetate copolymer comprises an ethylene content. In still otherexamples, the at least one ethylene vinyl acetate copolymer is at leastpartially unsaturated (e.g., comprises ethylenic unsaturation). In someexamples, the pre-foam composition comprises about 20 wt. % to about 60wt. % (e.g., from about 25 wt. % to about 50 wt. %; about 30 wt. % toabout 50 wt. %; about 40 wt. % to about 60 wt. %; about 30 wt. % toabout 60 wt. %; or about 45 wt. % to about 60 wt. %) of the at least oneethylene vinyl acetate copolymer. A suitable ethylene vinyl acetatecopolymer includes EVLAX® 40L-03 ethylene vinyl acetate resin availablefrom E.I. DuPont de Nemours Co., Wilmington, Del. Other suitableethylene vinyl acetate copolymers include EVATHENE® UE659 and EVATHENE®UE3300 ethylene vinyl acetate copolymers available from USI Corporation,Taiwan, ROC.

In some examples, the pre-foam compositions comprise about 1 to about 10wt. % of a first ethylene vinyl acetate copolymer and about 5 to about50 wt. % of a second ethylene vinyl acetate copolymer, wherein the wt. %amounts are relative to the weight of the pre-foam composition.

In one example, when the at least one ethylene vinyl acetate copolymercomprises two different ethylene vinyl acetate copolymers, the at leasttwo different ethylene vinyl acetate copolymers can differ in at leastvinyl acetate content. Thus, for example, a first ethylene vinyl acetatecopolymer can comprise about 15 to about 40 mol % vinyl acetate (e.g.,from about 15 to about 30 mol %; about 25 to about 35 mol %; or about 20mol % to about 40 mol %) and a second ethylene vinyl acetate copolymercomprises about 15 to about 30 mol % (e.g., from about 15 to about 25mol %; about 20 mol % to about 30 mol %; or about 15 mol % to about 30mol %) vinyl acetate.

In particular examples, the pre-foam compositions described herein donot include an ethylene vinyl acetate copolymer (EVA). In other words,the pre-foam compositions described herein can be free of an EVAcomponent.

Alternatively, the pre-foam compositions described herein can comprisefrom about 5 phr to about 50 phr of the EVA component. The pre-foamcompositions can comprise from about 10 phr to about 45 phr of the EVAcomponent. The pre-foam compositions can comprise from about 20 phr toabout 45 phr of the EVA component. The pre-foam compositions cancomprise from about 25 phr to about 40 phr of the EVA component. Thepre-foam compositions can comprise from about 25 phr to about 35 phr ofthe EVA component. The pre-foam compositions can comprise from about 30phr to about 37 phr of the EVA component. As used herein, the EVAcomponent is understood to refer to all the ethylene vinyl acetatecopolymers present in the pre-foam composition. Thus, the concentrationof the EVA component in a pre-foam composition refers to the totalconcentration of each ethylene vinyl acetate copolymer present in thecomposition. In some pre-foam compositions, the EVA component can beformed of only a single ethylene vinyl acetate copolymer. In otherpre-foam compositions, the EVA component can be formed of a plurality ofdifferent ethylene vinyl acetate copolymers.

Particular ratios of the components of the pre-foam compositions havebeen found to produce foams having beneficial properties. As used hereinand unless otherwise indicated or dictated by context, the ratio of afirst component to a second component is understood to the parts perhundred of resin (phr) of the first component divided by the phr of thesecond component present in the composition. In some aspects, a sum ofratios is presented, which is understood to mean the sum of the specificratios described.

The composition can be a composition having a ratio of the styreniccopolymer component to the unsaturated olefin component of about 0.1 toabout 1.0. The ratio of the styrenic copolymer component to theunsaturated olefin component can be from about 0.05 to about 0.40. Theratio of the styrenic copolymer component to the unsaturated olefincomponent can be from about 0.1 to about 0.3. The ratio of the styreniccopolymer component to the unsaturated olefin component can be fromabout 0.15 to about 0.32.

The composition can be a composition having a ratio of the styreniccopolymer component to the EVA component of about 0.2 to about 2.0. Theratio of the styrenic copolymer component to the EVA component can befrom about 0.3 to about 1.0. The ratio of the styrenic copolymercomponent to the EVA component can be from about 0.3 to about 0.8. Theratio of the styrenic copolymer component to the EVA component can befrom about 0.35 to about 0.72.

The composition can be a composition having a ratio of the unsaturatedolefin component to the EVA component of about 2.0 to about 4.0. Theratio of the unsaturated olefin component to the EVA component can befrom about 1.5 to about 3.0. The ratio of the unsaturated olefincomponent to the EVA component can be from about 1.5 to about 2.5. Theratio of the unsaturated olefin component to the EVA component can befrom about 2.0 to about 2.5.

In some aspects, a ratio I of a total parts by weight of the olefiniccopolymers present in the composition to a total parts by weight of theA-B-A block copolymer or partially hydrogenated thermoplasticelastomeric block copolymers present in the composition is from about0.65 to about 7.00, about 0.65 to 2.00, about 0.8 to 2.00, about 0.8 to7.00, about 1.00 to 2.00, about 2.00 to 3.00, about 1.00 to 3.00, about0.8 to 3.00, or about 0.65 to 3.00.

In some aspects, a ratio II of a total parts by weight of the linkingpolymers present in the composition to a total parts by weight of theA-B-A block copolymer or partially hydrogenated thermoplasticelastomeric block copolymers present in the composition is from about0.40 to 3.50, about 0.40 to 3.25, about 1.00 to 3.50, about 1.00 to3.25, about 1.00 to 3.00, about 1.2 to 2.8, about 1.25 to 3.25, about2.00 to 3.00, about 2.00 to 3.50, or about 1.00 to 2.00.

In some aspects, a ratio III of a total parts by weight of the EVAcopolymers present in the composition to a total parts by weight of theA-B-A block copolymer or partially hydrogenated thermoplasticelastomeric block copolymers present in the composition is from about1.00 to 5.00, about 1.00 to 2.00, about 2.00 to 3.00, about 3.00 to4.00, about 4.00 to 5.00, about 3.00 to 5.00, about 3.50 to 5.00, about4.00 to 5.00, or about 3.50 to 4.50.

In some aspects, a ratio IV of a total parts by weight of the linkingpolymers present in the composition to a total parts by weight of theA-B-A block copolymers or partially hydrogenated thermoplasticelastomeric block copolymers present in the composition is from about1.00 to 10.00, about 1.00 to 5.00, about 3.00 to 10.00, about 3.00 to5.00, about 3.50 to 5.00, about 3.00 to 4.00, or about 4.00 to 5.00.

In some aspects, a ratio V of a total parts by weight of the one or moreEVA copolymers present in the composition to a total parts by weight ofthe one or more olefinic copolymers present in the composition is fromabout 1.00 to 10.00, about 2.00 to 10.00, about 2.00 to 5.00, about 1.00to 5.00, about 1.50 to 5.00, about 2.50 to 5.00, about 2.50 to 4.50, orabout 2.00 to 4.50.

In some aspects, a ratio VI of a total parts by weight of the one ormore EVA copolymers present in the composition to a total parts byweight of the one or more linking polymers present in the composition isabout 1.00 to 2.00, about 0.50 to 5.00, about 0.50 to 3.00, about 1.00to 3.00, about 1.00 to 5.00, or about 1.20 to 2.00.

In some aspects, a sum of ratio I, II, III, IV, and V is from about 1.00to 10.00, about 1.00 to 2.00, about 2.00 to 3.00, about 3.00 to 4.00,about 4.00 to 5.00, about 5.00 to 6.00, about 6.00 to 7.00, about 7.00to 8.00, about 8.00 to 9.00, about 9.00 to 10.00, about 2.50 to 7.50,about 3.50 to 7.50, about 3.50 to 5.00, about 2.50 to 5.00, or about2.75 to 4.50.

In some aspects, a sum of ratio I, II, III, IV, V and VI is from about1.50 to 16.00, about 5.00 to 16.00, about 10.00 to 16.00, about 14.00 to16.00, about 14.00 to 15.00, about 10.00 to 15.00, about 5.00 to 10.00,about 1.50 to 5.00, or about 12.00 to 15.00.

When the composition includes an EVA component, the composition can havea sum of the ratio of the styrenic copolymer component to theunsaturated olefin component, of the ratio of the styrenic copolymercomponent to the EVA component, and of the ratio of the unsaturatedolefin component to the EVA component of about 1.5 to about 4.5. The sumof the ratios for the composition can be from about 2.0 to about 4.5.The sum of the ratios for the composition can be from about 2.2 to about3.8. The sum of the ratios for the composition can be from about 2.5 toabout 3.5.

It has been found that, in some aspects, a ratio II of a total parts byweight of the A-B-A block copolymer present in the composition to atotal parts by weight of the linking polymer present in the compositionhas a strong impact on the desired softness and energy return of thefoamed compositions. In some aspects, foam compositions having animproved softness and energy return can be formed from compositionshaving a ratio II from about 1.00 to 5.00, about 1.00 to 4.00, about1.50 to 4.00, about 1.50 to 3.50, about 1.00 to 3.00, or about 2.00 to4.00.

The compositions of the various examples described herein can alsocomprise a blowing agent, a free-radical initiator or combinationsthereof.

The blowing agent can be any appropriate type of physical blowing agentknown in the art including nitrogen, carbon dioxide, hydrocarbons (e.g.,propane, pentane, isopentane, and cyclopentane), chlorofluorocarbons,noble gases (e.g., helium (He), neon (Ne), argon (Ar), krypton (Kr), andxenon (Xe)) and/or mixtures thereof. In one example, the blowing agentcomprises nitrogen. The blowing agent may be supplied in any flowablephysical state such as a gas, a liquid, or a supercritical fluid.According to one example, a blowing agent source provides a blowingagent (e.g., carbon dioxide, nitrogen, and methanol) that is in asupercritical fluid state upon contacting (e.g., injection into) thepre-foam compositions of the various examples described herein, e.g.,when the pre-foam compositions are formed in an extruder (e.g., atwin-screw extruder).

Alternatively, the blowing agent can be any appropriate type of chemicalblowing agent known in the art including carbonates (e.g., ammoniumcarbonate and carbonates of alkali metals), azo compounds, diazocompounds, and combinations thereof. Chemical blowing agents include2,2′-azobis(2-cyanobutane), 2,2′-azobis(methylbutyronitrile),azodicarbonamide, p,p′-oxybis(benzene sulfonyl hydrazide), p-toluenesulfonyl semicarbazide, p-toluene sulfonyl hydrazide, and combinationsthereof. In the case of chemical blowing agents, gaseous products (e.g.,nitrogen gas) and other by-products are formed by a chemicalreaction(s), promoted by the process or by a reacting polymer'sexothermic heat. Since the blowing reaction occurs forming low molecularweight compounds acting as the blowing gas, additional exothermic heatmay also be released.

In some examples, the compositions described herein may require atemperature (e.g., from heating) of from about 130° C. to about 210° C.(e.g., from about 150° C. to about 190° C. or 165° C. to about 195°C.—such as temperatures to which an extruder and/or a mold might beheated) to “trigger” the chemical blowing agent to “decompose” toproduce the gas(es) necessary to transform the pre-foam compositions ofthe various examples described herein into the foam compositions of thevarious examples described herein.

Examples of blowing agents include UNICELL brand blowing agents, such asUNICELL-D600 MT, available from Dongjin Semichem Co., Ltd., Seoul,Korea.

In some examples, a combination of physical and chemical blowing agentscan be used.

The pre-foam compositions of the various examples described herein canalso comprise metal oxides, organic acids, fillers, nucleating agents,and combinations thereof. Examples of metal oxides include zinc oxide,titanium dioxide, and combinations thereof. Examples of organic acidsinclude C₃-C₃₀-alkanoic acids (e.g., C₁₄-C₃₀-alkanoic acids such asfatty acids) such as stearic acid and combinations of two or moreC₃-C₃₀-alkanoic acids. Calcium carbonate is an example of a materialwhich can be used both as a filler and as a nucleating agent.

The pre-foam compositions of the various examples described herein canalso comprise one or more crosslinking agents. Examples of crosslinkingagents include aliphatic unsaturated amides, such as methylenebisacryl-or -methacrylamide or ethylenebisacrylamide; aliphatic esters of polyolsor alkoxylated polyols with ethylenically unsaturated acids, such asdi(meth)acrylates or tri(meth)acrylates of butanediol or ethyleneglycol, polyglycols or trimethylolpropane; di- and triacrylate esters oftrimethylolpropane; acrylate and methacrylate esters of glycerol andpentaerythritol; allyl compounds, such as allyl (meth)acrylate,alkoxylated allyl (meth)acrylate, triallyl cyanurate, triallylisocyanurate, maleic acid diallyl ester, poly-allyl esters, vinyltrimethoxysilane, vinyl triethoxysilane, polysiloxane comprising atleast two vinyl groups, tetraallyloxyethane, tetraallyloxyethane,triallylamine, and tetraallylethylenediamine. Mixtures of thecrosslinking agents can also be employed.

The pre-foam compositions of the various examples described herein canalso comprise one or more free-radical initiators, such as an organicperoxide, a diazo compound (e.g., those described in U.S. Pat. No.6,303,723, which is incorporated by reference as if fully set forthherein) or combinations of two or more free-radical initiators. Examplesof organic peroxides that can be used as free-radical initiators includedicumyl peroxide; n-butyl-4,4-di(t-butylperoxy) valerate;1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane;2,5-dimethyl-2,5-di(t-butylperoxy) hexane; di-t-butyl peroxide;di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide;2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3;di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoylperoxide; t-butyl hydroperoxide; and combinations thereof.

The pre-foam compositions of the various examples described herein canbe solids or liquids at a temperature of about 25° C.

The pre-foam compositions of the various examples described herein canbe crosslinked to form crosslinked pre-foam compositions. The pre-foamcompositions can be crosslinked using various methods, includingchemical crosslinking methods or crosslinking methods using actinicradiation (e.g., thermal radiation, UV light, electron beam and gammaradiation). Such compositions comprise, in some examples, a polymercomprising styrene repeating units and non-styrenic repeating units, thepolymer crosslinked with a C₄-C₁₀₀ unsaturated-olefin block copolymercomprising blocks of C₄-C₁₀₀ unsaturated-olefin olefin. The crosslinkingbetween the polymer comprising styrene repeating units and non-styrenicrepeating units and the C₄-C₁₀₀ unsaturated olefin block copolymer canoccur directly between the molecules of the polymer comprising styrenerepeating units and non-styrenic repeating units and the C₄-C₁₀₀unsaturated olefin block copolymer, for example, without an “external”crosslinking agent such as the one or more crosslinking agents describedherein. The crosslinking between the polymer comprising styrenerepeating units and non-styrenic repeating units and the C₄-C₁₀₀unsaturated olefin block copolymer can also occur with an “external”crosslinking agent, such as the one or more crosslinking agentsdescribed herein.

Those of ordinary skill in the art will also recognize that there can beintramolecular crosslinking occurring between portions of a polymercomprising styrene repeating units and non-styrenic repeating unitsmolecule or portions of a C₄-C₁₀₀ unsaturated olefin block copolymer.This crosslinking can occur in the presence or in the absence of an“external” crosslinking agent such as the one or more crosslinkingagents described herein.

In some examples, the pre-foam compositions of the various examplesdescribed herein can be crosslinked to form crosslinked pre-foamcompositions in the presence of a blowing agent (e.g., a chemicalblowing agent or a physical blowing agent, as described herein).

In some examples, the crosslinked pre-foam compositions of the variousexamples described herein can be solids or liquids, but generally aresolids (e.g., thermoplastic solids) at a temperature of about 25° C. orhigher (e.g., at a temperature of from about 25° C. to about 220° C. anda pressure of from about 500 kPa to about 100 MPa). In some examples,the foam compositions of the various examples described herein aregenerally are solids (e.g., thermoplastic solids) at a temperature ofabout 25° C. or higher (e.g., at a temperature of from about 25° C. toabout 220° C. and a pressure of from about 500 kPa to about 100 MPa).

In some examples, the crosslinked pre-foam compositions of the variousexamples described herein can further comprise at least one ethylenevinyl acetate copolymer and/or at least one olefin block copolymer, aseach of the terms is defined herein.

Foam compositions are also contemplated herein and are interchangeablycalled “foam preforms.” As used herein, the term “foam compositions”refers to:

-   -   a crosslinked pre-foam composition that is foamed (e.g., foamed        using a blowing agent (physical and/or chemical)) before        crosslinking, after crosslinking or substantially simultaneously        with crosslinking; or    -   combinations of a pre-foam composition and a crosslinked        pre-foam composition (e.g., a combination of a pre-foam        composition and a crosslinked pre-foam composition, wherein the        combination is foamed (e.g., foamed using a blowing agent        (physical and/or chemical)) after the combination is formed        either after mixing two such compositions or after partially        crosslinking the pre-foam composition, such that some        crosslinked pre-foam composition is formed in situ).

In some examples, the foam compositions of the various examplesdescribed herein can further comprise at least one ethylene vinylacetate copolymer and/or at least one olefin block copolymer, as each ofthe terms is defined herein.

Some foam compositions of the various examples described herein (e.g.,foam compositions comprising a polymer comprising styrene repeatingunits and non-styrenic repeating units, crosslinked with a C₄-C₁₀₀unsaturated olefin) can form solid (e.g., thermoplastic) foam materials.These thermoplastic foam materials can be used as “foam preforms” andthe foam preforms can subsequently be compression molded. The foamcompositions of the present disclosure can have a density of about 0.08g/cm³ to about 0.15 g/cm³ (e.g., from about 0.10 g/cm³ to about 0.12g/cm³). In some examples, such foam preforms have an energy return fromabout 60% to about 85% (e.g., from about 65% to about 80%; about 65% toabout 75%; about 70% to about 80%; or about 75% to about 80%).

Some foam compositions of the various examples described herein (e.g.,foam preforms) can be compression molded to form compression moldedfoam. Such compression molded foam can have a density of from about 0.15g/cm³ to about 0.30 g/cm³ (e.g., from about 0.15 g/cm³ to about 0.2g/cm³).

Definitions

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. It will be further understoodthat terms, such as those defined in commonly used dictionaries, shouldbe interpreted as having a meaning that is consistent with their meaningin the context of the specification and relevant art and should not beinterpreted in an idealized or overly formal sense unless expresslydefined herein.

All publications, patents, and patent applications cited in thisspecification are cited to disclose and describe the methods and/ormaterials in connection with which the publications are cited. All suchpublications, patents, and patent applications are herein incorporatedby references as if each individual publication or patent werespecifically and individually indicated to be incorporated by reference.Such incorporation by reference is expressly limited to the methodsand/or materials described in the cited publications, patents, andpatent applications and does not extend to any lexicographicaldefinitions from the cited publications, patents, and patentapplications. Any lexicographical definition in the publications,patents, and patent applications cited that is not also expresslyrepeated in the instant specification should not be treated as such andshould not be read as defining any terms appearing in the accompanyingclaims.

Although any methods and materials similar or equivalent to thosedescribed herein can also be used in the practice or testing of thepresent disclosure, the preferred methods and materials are nowdescribed. Functions or constructions well-known in the art may not bedescribed in detail for brevity and/or clarity. Aspects of the presentdisclosure will employ, unless otherwise indicated, techniques ofnanotechnology, organic chemistry, material science and engineering andthe like, which are within the skill of the art. Such techniques areexplained fully in the literature.

It should be noted that ratios, concentrations, amounts, and othernumerical data can be expressed herein in a range format. Where thestated range includes one or both of the limits, ranges excluding eitheror both of those included limits are also included in the disclosure,e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well asthe range greater than ‘x’ and less than ‘y’. The range can also beexpressed as an upper limit, e.g. ‘about x, y, z, or less’ and should beinterpreted to include the specific ranges of ‘about x’, ‘about y’, and‘about z’ as well as the ranges of ‘less than x’, less than y’, and‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ shouldbe interpreted to include the specific ranges of ‘about x’, ‘about y’,and ‘about z’ as well as the ranges of ‘greater than x’, greater thany’, and ‘greater than z’. In addition, the phrase “about ‘x’ to ‘y’”,where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about‘y’”. It is to be understood that such a range format is used forconvenience and brevity, and thus, should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. To illustrate, anumerical range of “about 0.1% to 5%” should be interpreted to includenot only the explicitly recited values of about 0.1% to about 5%, butalso include individual values (e.g., 1%, 2%, 3%, and 4%) and thesub-ranges (e.g., 0.5%, 1.1%, 2.4%, 3.2%, and 4.4%) within the indicatedrange.

The term “about,” as used herein, can include traditional roundingaccording to significant figures of the numerical value. In someaspects, the term about is used herein to mean a deviation of 10%, 5%,2.5%, 1%, 0.5%, 0.1%, 0.01%, or less from the specified value.

The articles “a” and “an,” as used herein, mean one or more when appliedto any feature in aspects of the present disclosure described in thespecification and claims. The use of “a” and “an” does not limit themeaning to a single feature unless such a limit is specifically stated.The article “the” preceding singular or plural nouns or noun phrasesdenotes a particular specified feature or particular specified featuresand may have a singular or plural connotation depending upon the contextin which it is used.

As used herein, the term “units” can be used to refer to individual(co)monomer units such that, for example, styrenic repeat units refersto individual styrene (co)monomer units in the polymer. In addition, theterm “units” can be used to refer to polymeric block units such that,for example, “styrene repeating units” can also refer to polystyreneblocks; “units of polyethylene” refers to block units of polyethylene;“units of polypropylene” refers to block units of polypropylene; “unitsof polybutylene” refers to block units of polybutylene, and so on. Suchuse will be clear from the context.

EXAMPLES

Now having described the aspects of the present disclosure, in general,the following Examples describe some additional aspects of the presentdisclosure. While aspects of the present disclosure are described inconnection with the following examples and the corresponding text andfigures, there is no intent to limit aspects of the present disclosureto this description. On the contrary, the intent is to cover allalternatives, modifications, and equivalents included within the spiritand scope of the present disclosure.

Materials

The materials referred to throughout the examples are, unless otherwiseindicated, described in Table 1 below. The partially hydrogenated SEBSblock copolymers from Asahei Kasei (marketed under the trade nameTUFTEC®) all have an elongation at break of greater than 650% whenmeasured using ASTM D638. The P1083 (and the research grade JT-83) havea styrene content of about 20%, while the P5051 has a styrene content ofabout 47%. The SEBS copolymer from KRATON Polymers (KRATON® G1651E) hasa styrene content of about 30%-33%. The ENGAGE® polyolefin elastomersare copolymers of ethylene and octene, while the TAFMER® linkingpolymers are random copolymers of ethylene and 1-butene. For materialswhere the supplier is not listed in Table 1 (e.g. stearic acid), thesematerials are generally available from a variety of suppliers.

TABLE 1 Materials Used In Examples Trade Name Ingredient DescriptionSupplier TUFTEC ® P1083 Partially hydrogenated Aromatic/aliphatic AsaheiKasei SEBS block copolymer copolymer TUFTEC ® JT-83 Partiallyhydrogenated Aromatic/aliphatic Asahei Kasei (research grade of SEBSblock copolymer copolymer P1083) TUFTEC ® P5051 Partially hydrogenatedAromatic/aliphatic Asahei Kasei SEBS block copolymer copolymer KRATON ®G1651E partially hydrogenated Aromatic/aliphatic KRATON SEBS blockcopolymer copolymer Polymers Group INFUSE ™ 9000 OBC Olefin blockcopolymer Olefinic Copolymer Dow Chemical Co. INFUSE ™ 9107 OBC Olefinblock copolymer Olefinic Copolymer Dow Chemical Co. INFUSE ™ 9530 OBCOlefin block copolymer Olefinic Copolymer Dow Chemical Co. ENGAGE ® 8480Polyolefin elastomer Olefinic Copolymer Dow Chemical Co. ENGAGE ® 8540Polyolefin elastomer Olefinic Copolymer Dow Chemical Co. ENGAGE ® 8440Polyolefin elastomer Olefinic Copolymer Dow Chemical Co. TAFMER ® DF-110Alpha-olefin copolymer Linking Polymer Mitsui Elastomers TAFMER ® DF-605Alpha-olefin copolymer Linking Polymer Mitsui Elastomers EVA-659Ethylene vinyl acetate Ethylene vinyl acetate USI copolymer (EVA)Corporation EVA-3330 Ethylene vinyl acetate EVA USI copolymerCorporation ELVAX ® 360 Ethylene vinyl acetate EVA DuPont copolymerST/AC Stearic Acid Organic acid ZnO Zinc oxide Metal oxide TiO₂ TitaniumDioxide Metal oxide CaCO₃ Calcium Carbonate Filler/Nucleating AgentTAC-50GR Triallyl cyanurate Crosslinking agent Color base Coloring agent27020 Blue tint Coloring agent EVA 1375 Red pigment Coloring agent 8502Black pigment Coloring agent R929 Coloring agent UNICELL D600-MT Blowingagent Tramaco (MB-50%) JTR/TL Blowing agent Kumyang COLINK 101-45GE2,5-Dimethyl-2,5- Free-radical initiator di(tert- butylperoxy)hexane DCPDicumyl peroxide Free-radical initiator

Example 1: Batch Process of Preparing Compositions Capable of BeingFoamed

The pre-foam compositions, compositions prior to being foamed, describedin Tables 3 and 4 were prepared. Some of the pre-foam compositions werefirst compounded using the components shown in Table 2 to form pre-foambase compositions (PFBC) 1 and PFBC 2, according to Example 1. ThesePFBCs were then used to prepare the foam compositions shown in Tables 3,4. The properties of the foam compositions are described in Table 5. Insome instances, PFC 1 or PFBC 2 were further modified as shown in Tables3, 4 and 5 by adding additional materials. Other formulations wereprepared directly, without first forming a pre-foam base composition.

TABLE 2 Composition of Pre-Foam Base Compositions Used For MakingPre-Foam Compositions Pre-Foam Pre-Foam Base Base FormulationsComposition 1 Composition 2 A, B, C (PFBC 1) (PFBC 2) and D phr in phrin phr in Trade Name PFBC1 PFBC2 formulation TUFTEC ® P1083 10.0 16.6 **TUFTEC ® P5051 0.0 0.0 ** TUFTEC ® JT-83 0.0 0.0 ** KRATON ® D G1651E0.0 0.0 ** INFUSE ™ OBC9000 0.0 0.0 ** INFUSE ™ OBC9107 15.0 24.9 **INFUSE ™ OBC9507 0.0 0.0 ** INFUSE ™ OBC9530 0.0 0.0 ** ENGAGE ® 84800.0 0.0 ** ENGAGE ® 8540 0.0 0.0 ** ENGAGE ® 8440 0.0 0.0 ** TAFMER ®DF-110 12.0 19.9 ** TAFMER ® DF-605 18.0 29.9 ** EVA-659 40.0 0.0 **EVA-3330 5.0 0.0 ** ELVAX ® 360 0.0 0.0 ** ELVAX ® 40L-03 0.0 0.0 **ST/AC 1.0 1.7 0.0 ZnO 0.8 1.4 1.5 TiO₂ 0.0 0.0 3.6 CaCO₃ 0.0 0.0 5.0TAC-50GR 0.3 0.5 0.0 Color base 11.0 18.3 0.0 27020 0.0 0.0 0.0 EVA 13750.0 0.0 0.0 8502 0.0 0.0 0.0 R929 0.0 0.0 0.1 UNICELL D600-MT 11.5 11.50.0 JTR/TL 0.0 0.0 9.8 COLINK 101-45GE 0.0 0.0 0.0 DCP 0.7* 0.7* 0.7*concentration in formulation **: See Table 2 and 3

The pre-foam compositions were formed using a batch process where thepartially hydrogenated SEBS block copolymer and the olefin polymer werecombined in a kneader for about 20 minutes. During this time, thekneader temperature was maintained at a temperature of from about 100°C. to about 120° C. In some examples, the ethylene vinyl acetatecopolymer (the EVA component of the composition) and/or pigments wasadded to the mixture the partially hydrogenated SEBS block copolymer andthe olefin polymer.

Next, where present, the one or more metal oxide, one or more organicacid, and one or more crosslinking agent were added to the mixture. Thecombined mixture including the partially hydrogenated SEBS blockcopolymer and the olefin polymer, as well as (if present) the EVA alongwith the metal oxide, organic acid, and crosslinking agent were mixed inthe kneader for about 20 minutes, while the kneader temperature was heldat a temperature of from about 100° C. to about 120° C.

Next, the kneader temperature was lowered to about 90° C. or below. Thecombined mixture in the kneader was then combined with the blowing agentand a free radical initiator. The kneaded mixture was then subjected topelletization using a die that is cooled to maintain the temperature atabout 90° C. or below.

TABLE 3 Composition of foams A B C D E Composition Parts by Parts byParts by Parts by Parts by Material Wt. Wt. Wt. Wt. Wt. PFBC 1 (MB1) 0.00.0 0.0 0.0 0.0 PFBC 2 (MB2) 0.0 0.0 0.0 0.0 70.0 Kraton G1651E 0.0 0.00.0 0.0 0.0 TUFTEC ® P1083 0.0 0.0 0.0 0.0 9.3 TUFTEC ® JT-83 20.0 20.020.0 20.0 10.0 TUFTEC ® P5051 0.0 0.0 0.0 0.0 0.0 INFUSE ™ 9000 OBC 0.00.0 0.0 0.0 0.0 INFUSE ™ 9107 OBC 0.0 0.0 0.0 0.0 13.9 INFUSE ™ 9530 OBC0.0 0.0 0.0 20.0 20.0 ENGAGE ® 8440 0.0 0.0 20.0 0.0 0.0 ENGAGE ® 848020.0 0.0 0.0 0.0 0.0 ENGAGE ® 8540 0.0 20.0 0.0 0.0 0.0 TAFMER ® DF-1100.0 0.0 0.0 0.0 11.1 TAFMER ® DF-605 0.0 0.0 0.0 0.0 16.7 EVA-659 0.00.0 0.0 0.0 0.0 EVA-3330 0.0 0.0 0.0 0.0 0.0 ELVAX ® 360 60.0 60.0 60.060.0 0.0 ZnO 1.0 ST/AC 1.0 TAC-GR50 0.3 D600MT 8.9 DCP 0.0 101-45GE 0.9Total Parts by Wt. 120.7 120.7 120.7 120.7 112.0 F G H I J CompositionParts by Parts by Parts by Parts by Parts by Material Wt. Wt. Wt. Wt.Wt. PFBC 1 (MB1) 0.0 0.0 0.0 0.0 0.0 PFBC 2 (MB2) 90.0 70.0 100.0 50.080.0 Kraton G1651E 0.0 0.0 0.0 0.0 0.0 TUFTEC ® P1083 11.9 9.3 13.2 6.610.6 TUFTEC ® JT-83 10.0 10.0 0.0 10.0 0.0 TUFTEC ® P5051 0.0 0.0 0.020.0 0.0 INFUSE ™ 9000 OBC 0.0 0.0 0.0 0.0 0.0 INFUSE ™ 9107 OBC 17.913.9 19.9 9.9 15.9 INFUSE ™ 9530 OBC 0.0 20.0 0.0 20.0 20.0 ENGAGE ®8440 0.0 0.0 0.0 0.0 0.0 ENGAGE ® 8480 0.0 0.0 0.0 0.0 0.0 ENGAGE ® 85400.0 0.0 0.0 0.0 0.0 TAFMER ® DF-110 14.3 11.1 15.9 7.9 12.7 TAFMER ®DF-605 21.5 16.7 23.8 11.9 19.1 EVA-659 0.0 0.0 0.0 0.0 0.0 EVA-3330 0.00.0 0.0 0.0 0.0 ELVAX ® 360 0.0 0.0 0.0 0.0 0.0 ZnO 1.0 1.0 1.0 1.0 1.0ST/AC 1.0 1.0 1.0 1.0 1.0 TAC-GR50 0.2 0.4 0.4 0.3 0.4 D600MT 10.0 8.915.2 8.9 4.7 DCP 0.4 0.0 0.0 0.0 0.0 101-45GE 0.9 0.8 0.8 0.9 0.8 TotalParts by Wt. 113.5 112.1 118.4 112.0 107.9 K L M N O Composition Partsby Parts by Parts by Parts by Parts by Material Wt. Wt. Wt. Wt. Wt. PFBC1 (MB1) 0.0 0.0 0.0 0.0 0.0 PFBC 2 (MB2) 60.0 80.0 100.0 100.0 70.0Kraton G1651E 0.0 0.0 0.0 0.0 0.0 TUFTEC ® P1083 7.9 10.6 13.2 13.2 9.3TUFTEC ® JT-83 0.0 0.0 0.0 0.0 10.0 TUFTEC ® P5051 0.0 0.0 0.0 0.0 0.0INFUSE ™ 9000 OBC 0.0 0.0 0.0 0.0 20.0 INFUSE ™ 9107 OBC 11.9 15.9 19.919.9 13.9 INFUSE ™ 9530 OBC 40.0 20.0 0.0 0.0 0.0 ENGAGE ® 8440 0.0 0.00.0 0.0 0.0 ENGAGE ® 8480 0.0 0.0 0.0 0.0 0.0 ENGAGE ® 8540 0.0 0.0 0.00.0 0.0 TAFMER ® DF-110 9.5 12.7 15.9 15.9 11.1 TAFMER ® DF-605 14.319.1 23.8 23.8 16.7 EVA-659 0.0 0.0 0.0 0.0 0.0 EVA-3330 0.0 0.0 0.0 0.00.0 ELVAX ® 360 0.0 0.0 0.0 0.0 0.0 ZnO 1.0 1.0 1.0 1.0 1.0 ST/AC 1.01.0 1.0 1.0 1.0 TAC-GR50 0.4 0.4 0.4 0.4 0.3 D600MT 4.4 8.6 5.0 8.6 8.9DCP 0.0 0.0 0.0 0.0 0.0 101-45GE 0.8 0.8 0.8 0.8 0.9 Total Parts by Wt.107.6 111.8 108.2 111.8 112.0 P Q R S T Composition Parts by Parts byParts by Parts by Parts by Material Wt. Wt. Wt. Wt. Wt. PFBC 1 (MB1) 0.00.0 0.0 0.0 0.0 PFBC 2 (MB2) 70.0 100.0 60.0 70.0 100.0 Kraton G1651E0.0 0.0 0.0 0.0 0.0 TUFTEC ® P1083 9.3 13.2 7.9 9.3 13.2 TUFTEC ® JT-8310.0 0.0 0.0 10.0 0.0 TUFTEC ® P5051 0.0 0.0 0.0 0.0 0.0 INFUSE ™ 9000OBC 0.0 0.0 0.0 0.0 0.0 INFUSE ™ 9107 OBC 13.9 19.9 11.9 13.9 19.9INFUSE ™ 9530 OBC 20.0 0.0 40.0 20.0 0.0 ENGAGE ® 8440 0.0 0.0 0.0 0.00.0 ENGAGE ® 8480 0.0 0.0 0.0 0.0 0.0 ENGAGE ® 8540 0.0 0.0 0.0 0.0 0.0TAFMER ® DF-110 11.1 15.9 9.5 11.1 15.9 TAFMER ® DF-605 16.7 23.8 14.316.7 23.8 EVA-659 0.0 0.0 0.0 0.0 0.0 EVA-3330 0.0 0.0 0.0 0.0 0.0ELVAX ® 360 0.0 0.0 0.0 0.0 0.0 ZnO 1.0 1.0 1.0 1.0 1.0 ST/AC 1.0 1.01.0 1.0 1.0 TAC-GR50 0.3 0.4 0.4 0.4 0.4 D600MT 8.6 8.8 8.3 8.9 15.2 DCP0.0 0.0 0.0 0.0 0.0 101-45GE 0.9 0.8 0.8 0.8 0.8 Total Parts by Wt.111.8 116.5 111.5 112.1 118.4 U V′ W′ Composition Parts by Parts byParts by Material Wt. Wt. Wt. PFBC 1 (MB1) 100.0 100.0 100.0 PFBC 2(MB2) 0.0 0.0 0.0 Kraton G1651E 0.0 0.0 0.0 TUFTEC ® P1083 8.0 8.0 8.0TUFTEC ® JT-83 0.0 0.0 0.0 TUFTEC ® P5051 0.0 0.0 0.0 INFUSE ™ 9000 OBC0.0 0.0 0.0 INFUSE ™ 9107 OBC 12.0 12.0 12.0 INFUSE ™ 9530 OBC 0.0 0.00.0 ENGAGE ® 8440 0.0 0.0 0.0 ENGAGE ® 8480 0.0 0.0 0.0 ENGAGE ® 85400.0 0.0 0.0 TAFMER ® DF-110 9.6 9.6 9.6 TAFMER ® DF-605 14.4 14.4 14.4EVA-659 31.9 31.9 31.9 EVA-3330 4.0 4.0 4.0 ELVAX ® 360 0.0 0.0 0.0 ZnO1.0 1.0 1.0 ST/AC 1.0 1.0 1.0 TAC-GR50 0.4 1.0 0.6 D600MT 8.8 8.4 7.9DCP 0.0 0.0 0.0 101-45GE 0.8 0.2 0.6 Total Parts by Wt. 112.0 111.6111.1

Example 2: Continuous Process of Preparing Pre-Foam Compositions

Pre-foam compositions can be prepared using a continuous process wherethe styrenic copolymer component and the unsaturated olefin componentare pre-mixed in a hopper and fed into a twin-screw extruder. The zonein the twin-screw extruder into which the styrenic copolymer componentand the unsaturated olefin component are fed (ZONE 1) is held at atemperature of from about 100° C. to about 120° C. When included in thepre-foam composition, the optional EVA component and/or pigments arepre-mixed with the styrenic copolymer component and the unsaturatedolefin component.

Next, one or more metal oxide, one or more organic acid, and one or morecrosslinking agent are added to the mixture of polymer and unsaturatedolefin The particle size of the metal oxide used was less than 1 micron.The combined mixture of the styrenic copolymer component, theunsaturated olefin component, the optional EVA component, and the metaloxide, organic acid, and crosslinking agent are mixed in ZONE 1 of thetwin-screw extruder at a temperature of from about 100° C. to about 120°C. until thoroughly mixed.

The combined mixture of the styrenic copolymer component, the,unsaturated olefin component, the optional EVA component, and the metaloxide, organic acid, and crosslinking agent move to ZONE 2 of thetwin-screw extruder, where the temperature is about 90° C. or below. Thecombined mixture of the styrenic copolymer component, the unsaturatedolefin component, the EVA component, and the metal oxide, organic acid,and crosslinking agent are then combined in ZONE 2 with a blowing agentand a free radical initiator.

Next, the mixture of the styrenic copolymer component, the unsaturatedolefin component, the optional EVA component, and the metal oxide,organic acid, crosslinking agent, blowing agent, and free radicalinitiator is then subjected to pelletization using a die that is cooledto maintain the temperature at about 90° C. or below. The pelletizationcan performed under water, thus cooling the resulting pellets as theyexit the pelletization die.

Example 3: Forming Foam Articles from Pre-Foam Compositions

Pellets made according to the batch process described in Examples 1using the pre-foam composition formulations described in Tables 1-4 wereinjection molded (IM) into a pre-heated mold where the mold temperaturewas, from about 170° C. to about 180° C. The mold temperature was abovethe decomposition temperature of the chemical blowing agent, whichdecomposed producing gas in the softened composition and foaming it. Themold temperature was also above the initiation temperature of thefree-radical initiator, producing a polymerization reaction whichcrosslinked the unsaturated styrenic copolymer component with theunsaturated olefin component of the composition.

As indicated in Table 5, some of the pre-foam compositions were foamedand injection molded in a single-step process (IM) to produce thefinished molded foam article without a compression molding step, whileother pre-foam compositions were foamed and molded using a process inwhich the pre-foam composition was first injection molded to form amolded foam pre-foam, then the molded foam pre-form was annealed, andthen the annealed molded foam pre-form was compression molded to producethe finished molded foam article (IM+CM).

For the pre-foam compositions which were injection molded andsubsequently compression molded to produce the finished molded foamarticles (IM+CM), the injection molded foam preform was taken through anannealing process in which the foam preform was heated to a temperatureof about 70° C. to about 80° C. for about 10 to about 15 minutes; thencooled to a temperature of about 60° C. to about 70° C. and held at thattemperature for about 10 to about 15 minutes; next the preform wascooled to a temperature of about 50° C. to about 60° C. and held at thattemperature for about 10 to about 15 minutes; then cooled to atemperature of about 45° C. to about 55° C. and held at that temperaturefor about 10 to about 15 minutes. The annealed molded foam preform wasthen washed with water (about 35° C. to about 40° C.) for about 10 toabout 15 minutes and subsequently dried for 24 hours.

The annealed molded foam preform was then placed in a compression moldwhich is at least 10% smaller at least one dimension relative to itsinitial foamed, molded and annealed state prior to the compressionmolding. During the compression molding process, the foam preform isheated to a surface temperature of from about 130° C. to about 150° C.Then the foam preform is cooled to a surface temperature of about 30° C.in about 15 minutes or less (e.g., in about 12 minutes or less) to givea finished compression molded foam article.

While this experiment used the pre-foam compositions only to produceinjection molded foam articles (IM) and injection molded and compressionmolded foam articles (IM+CM) using the processes described above, thepre-foam compositions described herein can be foamed and/or molded usingother types of processes known in the art. For example, these pre-foamcompositions can be used to form slab foam, particulate (e.g., bead)foams, etc. These forms of foam can then be used in various ways. Forexample, slab foam can be formed, and then can be used as formed as afinal component, or can be compression molded to form a final component.Pellets of the pre-foam compositions can be used to form individualparticulate foams, or can be foamed and molded to form molded foamarticles.

TABLE 4 Compositions and Component Ratios for Foams Composition A B C DE Aromatic/Aliphatic Block 20.0 20.0 20.0 20.0 19.3 Copolymer (Parts byWt.) Olefinic Copolymer (Parts 20.0 20.0 20.0 20.0 33.9 by Wt.) LinkingPolymer (Parts by 0.0 0.0 0.0 0.0 27.8 Wt.) EVA Copolymer (Parts by 0.00.0 0.0 0.0 0.0 Wt.) Resin Component (Parts 40.0 40.0 40.0 40.0 81.0 byWt.) Component Ratios I: Olefinic Copolymer 1.00 1.00 1.00 1.00 1.76(Parts by Wt.) to Aromatic/Aliphatic Block Copolymer (Parts by Wt.) II:Linking Polymer (Parts 0.00 0.00 0.00 0.00 1.44 by Wt.) toAromatic/Aliphatic Block Copolymer (Parts by Wt.) III: EVA Copolymer(Parts 0.00 0.00 0.00 0.00 0.00 by Wt.) to Aromatic/Aliphatic BlockCopolymer (Parts by Wt.) IV: Linking Polymer (Parts 0.00 0.00 0.00 0.000.82 by Wt.) to Olefinic Copolymer (Parts by Wt.) V: EVA Copolymer(Parts 0.00 0.00 0.00 0.00 0.00 by Wt.) to Olefinic Copolymer (Parts byWt.) VI: EVA Copolymer (Part N/A N/A N/A N/A 0.00 by Wt.) to LinkingPolymer (Parts by Wt.) Sum of Ratios I-V 1.00 1.00 1.00 1.00 3.20 Sum ofRatios I-VI* N/A N/A N/A N/A 4.02 Composition F G H I JAromatic/Aliphatic Block 21.9 19.3 13.2 36.6 10.6 Copolymer (Parts byWt.) Olefinic Copolymer (Parts 17.9 33.9 19.9 29.9 35.9 by Wt.) LinkingPolymer (Parts by 35.7 27.8 39.7 19.9 31.8 Wt.) EVA Copolymer (Parts by0.0 0.0 0.0 0.0 0.0 Wt.) Resin Component (Parts 75.5 81.0 72.8 86.4 78.2by Wt.) Component Ratios I: Olefinic Copolymer 0.82 1.76 1.50 0.82 3.39(Parts by Wt.) to Aromatic/Aliphatic Block Copolymer (Parts by Wt.) II:Linking Polymer (Parts 1.63 1.44 3.00 0.54 3.00 by Wt.) toAromatic/Aliphatic Block Copolymer (Parts by Wt.) III: EVA Copolymer(Parts 0.00 0.00 0.00 0.00 0.00 by Wt.) to Aromatic/Aliphatic BlockCopolymer (Parts by Wt.) IV: Linking Polymer (Parts 2.00 0.82 2.00 0.660.89 by Wt.) to Olefinic Copolymer (Parts by Wt.) V: EVA Copolymer(Parts 0.00 0.00 0.00 0.00 0.00 by Wt.) to Olefinic Copolymer (Parts byWt.) VI: EVA Copolymer (Part 0.00 0.00 0.00 0.00 0.00 by Wt.) to LinkingPolymer (Parts by Wt.) Sum of Ratios I-V 2.45 3.20 4.50 1.36 6.39 Sum ofRatios I-VI* 4.45 4.02 6.50 2.02 7.28 Composition K L M N OAromatic/Aliphatic Block 7.9 10.6 13.2 13.2 19.3 Copolymer (Parts byWt.) Olefinic Copolymer (Parts 51.9 35.9 19.9 19.9 13.9 by Wt.) LinkingPolymer (Parts by 23.8 31.8 39.7 39.7 27.8 Wt.) EVA Copolymer (Parts by0.0 0.0 0.0 0.0 0.0 Wt.) Resin Component (Parts 83.7 78.2 72.8 72.8 61.0by Wt.) Component Ratios I: Olefinic Copolymer 6.54 3.39 1.50 1.50 0.72(Parts by Wt.) to Aromatic/Aliphatic Block Copolymer (Parts by Wt.) II:Linking Polymer (Parts 3.00 3.00 3.00 3.00 1.44 by Wt.) toAromatic/Aliphatic Block Copolymer (Parts by Wt.) III: EVA Copolymer(Parts 0.00 0.00 0.00 0.00 0.00 by Wt.) to Aromatic/Aliphatic BlockCopolymer (Parts by Wt.) IV: Linking Polymer (Parts 0.46 0.89 2.00 2.002.00 by Wt.) to Olefinic Copolymer (Parts by Wt.) V: EVA Copolymer(Parts 0.00 0.00 0.00 0.00 0.00 by Wt.) to Olefinic Copolymer (Parts byWt.) VI: EVA Copolymer (Part 0.00 0.00 0.00 0.00 0.00 by Wt.) to LinkingPolymer (Parts by Wt.) Sum of Ratios I-V 9.54 6.39 4.50 4.50 2.16 Sum ofRatios I-VI* 10.00 7.28 6.50 6.50 4.16 Composition P Q R S TAromatic/Aliphatic Block 19.3 13.2 7.9 19.3 13.2 Copolymer (Parts byWt.) Olefinic Copolymer (Parts 33.9 19.9 51.9 33.9 19.9 by Wt.) LinkingPolymer (Parts by 27.8 39.7 23.8 27.8 39.7 Wt.) EVA Copolymer (Parts by0.0 0.0 0.0 0.0 0.0 Wt.) Resin Component (Parts 81.0 72.8 83.7 81.0 72.8by Wt.) Component Ratios I: Olefinic Copolymer 1.76 1.50 6.54 1.76 1.50(Parts by Wt.) to Aromatic/Aliphatic Block Copolymer (Parts by Wt.) II:Linking Polymer (Parts 1.44 3.00 3.00 1.44 3.00 by Wt.) toAromatic/Aliphatic Block Copolymer (Parts by Wt.) III: EVA Copolymer(Parts 0.00 0.00 0.00 0.00 0.00 by Wt.) to Aromatic/Aliphatic BlockCopolymer (Parts by Wt.) IV: Linking Polymer (Parts 0.82 2.00 0.46 0.822.00 by Wt.) to Olefinic Copolymer (Parts by Wt.) V: EVA Copolymer(Parts 0.00 0.00 0.00 0.00 0.00 by Wt.) to Olefinic Copolymer (Parts byWt.) VI: EVA Copolymer (Part 0.00 0.00 0.00 0.00 0.00 by Wt.) to LinkingPolymer (Parts by Wt.) Sum of Ratios I-V 3.20 4.50 9.54 3.20 4.50 Sum ofRatios I-VI* 4.02 6.50 10.00 4.02 6.50 Composition U V′ W′Aromatic/Aliphatic Block 8.0 8.0 8.0 Copolymer (Parts by Wt.) OlefinicCopolymer (Parts 12.0 12.0 12.0 by Wt.) Linking Polymer (Parts by 23.923.9 23.9 Wt.) EVA Copolymer (Parts by 35.9 35.9 35.9 Wt.) ResinComponent (Parts 79.8 79.8 79.8 by Wt.) Component Ratios I: OlefinicCopolymer 1.50 1.50 1.50 (Parts by Wt.) to Aromatic/Aliphatic BlockCopolymer (Parts by Wt.) II: Linking Polymer (Parts 3.00 3.00 3.00 byWt.) to Aromatic/Aliphatic Block Copolymer (Parts by Wt.) III: EVACopolymer (Parts 4.50 4.50 4.50 by Wt.) to Aromatic/Aliphatic BlockCopolymer (Parts by Wt.) IV: Linking Polymer (Parts 2.00 2.00 2.00 byWt.) to Olefinic Copolymer (Parts by Wt.) V: EVA Copolymer (Parts 3.003.00 3.00 by Wt.) to Olefinic Copolymer (Parts by Wt.) VI: EVA Copolymer(Part 1.50 1.50 1.50 by Wt.) to Linking Polymer (Parts by Wt.) Sum ofRatios I-V 4.50 4.50 4.50 Sum of Ratios I-VI* 15.50 15.50 15.50 NT: nottested N/A: not applicable

Example 4: Testing of Foam Articles

Examples of foam articles formed from the formulations described inTables 3 and 4 were made and tested to determine their physicalproperties (e.g., specific gravity, hardness, split tear, compressionset, and energy return). The results for foam articles for the variousformulations are reported in Table 5.

The purpose of this experiment was to identify pre-foam compositionswith improved split-tear values as compared to conventional ethylenevinyl acetate (EVA) foam, but which otherwise maintained the physicalproperties of conventional EVA foam which are beneficial for us ascomponents of articles of footwear. The experimental pre-foamcompositions were based on using a styrenic copolymer component, anunsaturated olefin component, and optionally an EVA component. Some ofthe formulations were used to produce foams which were first injectionmolded and then annealed and compression molded to produce a final foamcomponent (IM+CM), while other formulations were used to produce foamswhich were injection molded to produce a final foam component (IM). Thetarget range for the split-tear values was from about 2.5 kg/cm to about3.0 kg/cm or greater. As a comparison, the split tear value forconventional EVA foam is about 1.7. The target ranges for the otherphysical properties of the final foam component were: a specific gravityof about 0.1 to about 0.2; an Asker C hardness of about 40 to about 50;a compression set of about 20% to about 35%; and a resilience of atleast about 60%. These target ranges were based primarily on thephysical properties of conventional EVA foam used as components forarticle of footwear, which has a specific gravity of from 0.080 to0.095, an Asker C hardness of 34-38, a compression set of 75%, and anresiliency of about 59.

The test method used to obtain the specific gravity values reported inTable 5 is as follows.

The specific gravity of the foam was be determined by testing 3representative samples taken from a foam preform or compression moldedfoam component. Using a balance with appropriate accuracy for the weightof the sample, the weight of each sample was determined both in air andwhen the sample was completely submerged in distilled water at atemperature of 22° C.±2° C., after removing any air bubbles adhered tothe surface of the foam sample before weighing. The specific gravity(S.G.) was then calculated by taking the weight of the sample in waterand subtracting that from the weight of the sample in air, and thisvalue was then divided into the weight of the sample in air, where allthe weights are weights in grams.

Split Tear Test

The test method used to obtain the split tear values for foam articlesas shown in Table 5 is as follows.

Four die-cut, rectangular-shaped samples of slab sheet or molded foamwere prepared, each measuring 2.54 cm×15.24 cm×10±1 mm (thickness). Ifthe foam material to be tested had a skin, the material had its skinremoved before preparing the four samples. A 3 cm long cut was made inthe center from one end of the sample. Then five successive 2 cmportions were marked on the sample.

The crosshead speed of the tensile test apparatus was set at 50 mm/min.Each separated end of the sample was clamped in an upper grip and alower grip of the test apparatus. The separation was placed in themiddle between both grips. Each section of the sample was held in aclamp in such a manner that the original adjacent cut edges formed astraight line joining the centers of the clamps.

As needed, the cut was aided with a sharp knife to keep separating thefoam material in the center of the sample. Readings caused by cuttingwith the knife were discarded. The lowest values for each of the fiveportions of each sample were recorded in kg/cm. Five values wererecorded for each sample and an average of the five values was thenobtained and reported. If a portion of a sample included a portionhaving an air bubble more than 2 mm in diameter, the value for theportion including the air bubble was not included in the average. Ifmore than one portion of a sample was found to include air bubbleshaving a diameter greater than 2 mm, another sample was then tested.

Durometer Hardness Test

The test used to obtain the hardness values for the foam articlesreported in Table 5 is as follows.

For flat foams, the sample was a minimum of 6 mm thick for Asker Cdurometer testing. If necessary, foam samples were stacked to make upthe minimum thickness. Foam samples were large enough to allow allmeasurements to be performed at a minimum of 12 mm from the edge of thesample and at least 12 mm from any other measurement. Regions testedwere flat and parallel with an area at least 6 mm in diameter. For thesamples tested in Table 5, standard samples having dimensions ofapproximately 35 cm×13 cm×1.8 cm, were used, and a minimum of fivehardness measurements were taken and tested using a 1 kg head weight.

Compression Set

The test used to obtain the compression set values for foam articlesreported in Table 5 is as follows.

A foam sample was compressed between two metal plates to 50% of itsoriginal thickness and placed in an oven at 50° C. for 6 hours. Thesample was then cooled and the difference between its precompression andpost-compression thickness was used as the measure of static compressionset.

For the tests reported in Table 5, molded plaques having skin on oneside and a thickness of 10 mm were used to obtain the samples. Theplaque was then skived to a thickness of 10+/−0.5 mm to remove the skinbefore cutting the samples. Compression molded foam materials havingskin on two sides had the skin skived from one side, so that skinremained on only one side. Five 2.54 cm diameter circles were thenmachine drilled from the plaque to obtain the samples to be tested.

The compression set testing device consists of two flat steel plates setbetween the parallel faces of the compression device with compressionrings and spacer bars for each set of parallel faces. Four compressionrings of the same thickness (4.5 mm or 5.0 mm based on the specimenthickness) were used for each parallel face of the compression device.The percent compression set was calculated using the following equation:% Set=((Original gauge−final gauge)/(50% Original gauge))×100

The center area of each specimen was marked and used to measure thespecimens with the use of an AMES gage with no load on top.

Energy Return Test

The test used to obtain the energy return values for foam articlesreported in Table 5 is as follows.

Energy return of the foam articles was determined using ASTM D 2632 92,which uses a vertical rebound apparatus.

TABLE 5 Processing Methods and Properties of Foam Articles Composition AB C D E Processing Method 2 2 2 2 2 Physical Properties IM Foam SpecificGravity 0.1185 0.1166 0.1171 0.1153 0.11 Hardness (Asker C) 32-33 33-3432-33 28-30 41-42 Split Tear (kg/cm) 1.79-1.75 1.61-1.78 1.58-1.621.52-1.56 1.3 Compression Set (%) 72-73 70-71 72-74 70-71 51-53 EnergyReturn (slab) (%) NA IM + CM Foam Specific Gravity 0.2048 0.2089 0.20210.2042 0.16-0.17 Hardness (Asker C) 49-50 50-51 49-50 56-58 53-54 SplitTear (kg/cm) 2.7-2.8 2.6-2.8 2.8-2.9 2.4-2.5 2 Compression Set (%) 43-4539-40 49-50 38-39 21 Energy Return (slab) (%) 50-51 49-50 53-54 47-48 68Composition F G H I J Processing Method 2 2 1 2 2 Physical Properties IMFoam Specific Gravity 0.09 0.1 0.15 0.11 0.159 Hardness (Asker C) 32-3434-35 52-53 43-45 50-51 Split Tear (kg/cm) 1.9 2 2.5-2.6 1.6 2.98-3.06Compression Set (%) 71-72 74-76 35-55 69 49-51 Energy Return (slab) (%)60 83-89 71 64 64-65 IM + CM Foam Specific Gravity 0.13-0.14 NT NA 0.18NT Hardness (Asker C) 43-48 NT NA 55-59 NT Split Tear (kg/cm) 2.3 NT NA2.5-2.6 NT Compression Set (%) 39-41 NT NA 21-22 NT Energy Return (slab)(%) 68 NT NA 69 NT Composition K L M N O Processing Method 2 1 2 1 2Physical Properties IM Foam Specific Gravity 0.15 0.17 0.167 0.17 0.13Hardness (Asker C) 46-48 54-55 52-54 54-55 42-44 Split Tear (kg/cm)2.73-3.01 2.6-2.7 3.0-3.1 2.7-2.8 2 Compression Set (%) 59-61 26-3243-46 28-33 71 Energy Return (slab) (%) 67-72 69-70 61-63 69-72 65 IM +CM Foam Specific Gravity NT NA NT NA 0.17-0.18 Hardness (Asker C) NT NANT NA 54-57 Split Tear (kg/cm) NT NA NT NA 3.0-3.1 Compression Set (%)NT NA NT NA 28 Energy Return (slab) (%) NT NA NT NA 69 Composition P Q RS T Processing Method 2 1 1 1 1 Physical Properties IM Foam SpecificGravity 0.11 0.17 0.16 0.15 0.11 Hardness (Asker C) 42-43 54-55 51-5249-51 33-36 Split Tear (kg/cm) 2 3.4 2.6 2.8-3.0 1.4-1.7 Compression Set(%) 66-72 38-39 37-43 40-50 63-70 Energy Return (slab) (%) NA 68 71-7374-76 84-87 IM + CM Foam Specific Gravity 0.17 NA NA NA NA Hardness(Asker C) 52-55 NA NA NA NA Split Tear (kg/cm) 3.1 NA NA NA NACompression Set (%) 31-37 NA NA NA NA Energy Return (slab) (%) 67-70 NANA NA NA Composition U V′ W′ Processing Method 1 1 1 Physical PropertiesIM Foam Specific Gravity 0.18 0.19 0.19 Hardness (Asker C) 42-45 42-4443-45 Split Tear (kg/cm) 2.5-2.6 2.6-2.7 2.6 Compression Set (%) 29-3332-34 31-32 Energy Return (slab) (%) 78-80 80 79-82 IM + CM FoamSpecific Gravity NA NA NA Hardness (Asker C) NA NA NA Split Tear (kg/cm)NA NA NA Compression Set (%) NA NA NA Energy Return (slab) (%) NA NA NANT: not tested NA: not applicable 1: Pre-foam composition was injectionmolded to form final foam article 2: Pre-foam composition was injectionmolded to form foam preform, and then the foam preform was compressionmolded to form final foam article

Results

Four of the 13 final molded foam articles produced using injectionmolding and compression molding (IM+CM) had split tear values of greaterthan 2.5, and 8 of the 11 final molded foam articles produced using justthe injection molding process (IM) had split tear values of greater than2.5. Unexpectedly, 12 of the formulations which produced molded foamarticles with the target split tear values also had resiliency valuessignificantly higher than expected. Specifically, formulations H, I, L,N, O, P, Q, R, S, U, V and X had resiliency values ranging from 67% to82%. However, only 2 pre-foam compositions were found which producedfinal foam components having all their physical properties in the targetranges (formulations U and X). The resiliency values for these twoformulations were found to be over 14 percentage points greater than forconventional EVA foam.

In general, the pre-foam compositions which produced final foamcomponents with unexpectedly high resiliency values included from about10 parts per hundred of resin (phr) to about 22 phr of the styreniccopolymer component, and from about 45 phr to about 80 phr of theunsaturated olefin component. Some of these pre-form compositions alsocomprised from about 31 phr to about 36 phr of the EVA component, whileothers were free of the EVA component. Generally, the pre-foamcompositions which produced final foam components with target split tearvalues and unexpectedly high resiliency values had ratios of the phr ofthe styrenic copolymer component to the phr of the unsaturated olefincomponent which ranged from about 0.17 to about 0.30. For the pre-foamcompositions including an EVA component, the ratios of the phr of thestyrenic copolymer component to the phr of the EVA component ranged fromabout 0.37 to about 0.70. The ratios of the phr of the unsaturatedolefin component to the phr of the EVA component ranged from about 2.2to about 2.3. For the pre-foam compositions including an EVA component,the sum of all three ratios ranged from about 2.7 to about 3.3.

It should be emphasized that the above-described aspects of the presentdisclosure are merely possible examples of implementations, and are setforth only for a clear understanding of the principles of thedisclosure. Many variations and modifications may be made to theabove-described aspects of the disclosure without departingsubstantially from the spirit and principles of the disclosure. All suchmodifications and variations are intended to be included herein withinthe scope of this disclosure.

The present disclosure will be better understood upon review of thefollowing clauses, which should not be confused with the claims.

1. A composition comprising:

a block copolymer comprising

-   -   a first block and a third block, each independently comprising a        linear or branched chain aliphatic polymer having a plurality of        aromatic groups attached pendantly thereto,    -   a second block located between the first block and the third        block and comprising an aliphatic polymer having a plurality of        aliphatic side chains attached thereto, and    -   a plurality of first ethylenically unsaturated group present on        one or more of the first block, second block, and third block;

wherein the block copolymer comprises about 60% to about 90% of thesecond blocks by weight based upon the weight of the block copolymer;

an olefinic copolymer comprising a plurality of first olefinic segmentsand a plurality of second olefinic segments having a different chemicalstructure from the first olefinic segments;

one or more linking polymers, each linking polymer comprising one ormore third olefinic segments; and

an ethylene-vinyl acetate (EVA) copolymer.

wherein a sum of a ratio I, II, III, IV, and V is from about 1.00 toabout 10.00;

wherein the ratio I is a ratio of a total parts by weight of theolefinic copolymers present in the composition to a total parts byweight of the block copolymer present in the composition;

wherein the ratio II is a ratio of a total parts by weight of thelinking polymers present in the composition to a total parts by weightof the block copolymer present in the composition;

wherein the ratio III is ratio of a total parts by weight of the EVAcopolymers present in the composition to a total parts by weight of theblock copolymer present in the composition;

wherein the ratio IV is a ratio of the total parts by weight of thelinking polymers present in the composition to a total parts by weightof the block copolymers present in the composition, and

wherein the ratio V is a ratio of the total parts by weight of the oneor more EVA copolymers present in the composition to a total parts byweight of the one or more olefinic copolymers present in thecomposition.

2. The composition according to clause 1, wherein the sum of ratio I,II, III, IV, and V is from about 3.50 to about 5.00.

3. A composition comprising:

a block copolymer comprising

-   -   a first block and a third block, each independently comprising a        linear or branched chain aliphatic polymer having a plurality of        aromatic groups attached pendantly thereto,    -   a second block located between the first block and the third        block and comprising an aliphatic polymer having a plurality of        aliphatic side chains attached thereto, and    -   a plurality of first ethylenically unsaturated group present on        one or more of the first block, second block, and third block;

wherein the block copolymer comprises about 60% to about 90% of thesecond blocks by weight based upon the weight of the block copolymer;

an olefinic copolymer comprising a plurality of first olefinic segmentsand a plurality of second olefinic segments having a different chemicalstructure from the first olefinic segments; and

one or more linking polymers, each linking polymer comprising one ormore third olefinic segments.

4. A composition comprising:

an A-B-A block copolymer, wherein each of the A blocks comprise styrenicrepeat units, the B block is a random copolymer of ethylene and analpha-olefin having about 3 to 8 carbon atoms, and wherein theA-B-A-block copolymer comprises about 10% to about 40% of the A blocksby weight based upon the weight of the A-B-A block copolymer;

an olefinic block copolymer, wherein the olefinic block copolymer is acopolymer of ethylene and an alpha-olefin having about 6 to 12 carbonatoms, and wherein the olefinic block copolymer has one or more blocksrich in the ethylene and one or more blocks rich in the alpha-olefin;

an alpha-olefin linking polymer, wherein the alpha-olefin linkingpolymer is a copolymer of ethylene and an alpha-olefin having about 3 to8 carbon atoms, and wherein the alpha-olefin linking polymer has analpha-olefin monomer content of about 15% to about 40% by weight basedupon the weight of the alpha-olefin linking polymer; and

an ethylene-vinyl acetate copolymer having a vinyl acetate content ofabout 10% to about 40% by weight based upon the weight of theethylene-vinyl acetate copolymer.

5. The composition according to any one of clauses 1-4, wherein each ofthe A blocks consists essentially of polystyrene.

6. The composition according to any one of clauses 1-5, wherein the Bblock consists essentially of a copolymer of ethylene and octene.

7. The composition according to any one of clauses 1-5, wherein the Bblock consists essentially of a copolymer of ethylene and butadiene.

8. The composition according to any one of clauses 1-7, wherein thecomposition comprises a first alpha-olefin linking polymer and a secondalpha-olefin linking polymer,

wherein the first alpha-olefin linking polymer and the secondalpha-olefin linking polymer are copolymers of ethylene and 1-butene,each having a different ratio of ethylene to 1-butene monomer content inthe copolymer.

9. The composition according to any one of clauses 1-8, wherein thecomposition comprises about 5 parts by weight to about 15 parts byweight of the A-B-A block copolymer, about 10 parts by weight to about20 parts by weight of the olefinic block copolymer, about 25 parts byweight to about 35 parts by weight of the alpha-olefin linking polymers,and about 30 parts by weight to about 60 parts by weight of theethylene-vinyl acetate copolymer based upon the weight of the pre-foamcomposition.10. A composition comprising:

a partially hydrogenated thermoplastic elastomeric block copolymer, thepartially hydrogenated thermoplastic elastomeric block copolymercomprising:

-   -   one or more A blocks comprising aromatic repeat units,    -   one or more B blocks comprising aliphatic repeat units, and    -   one or more first ethylenically unsaturated groups present on        one or both of the aromatic repeat units and the aliphatic        repeat units;

an olefinic block copolymer, wherein the olefinic block copolymer is acopolymer of a first alpha-olefin and a second alpha-olefin differentfrom the first alpha-olefin, and wherein the olefinic block copolymercomprising one or more second ethylenically unsaturated groups;

an alpha-olefin linking polymer, wherein the alpha-olefin linkingpolymer comprises one or more aliphatic sidechains; and

an ethylene-vinyl acetate copolymer;

wherein a sum of a ratio I, II, III, IV, and V is from about 1.00 toabout 10.00;

wherein the ratio I is a ratio of a total parts by weight of theolefinic copolymers present in the composition to a total parts byweight of the partially hydrogenated thermoplastic elastomeric blockcopolymer present in the composition;

wherein the ratio II is a ratio of a total parts by weight of thealpha-olefin linking polymers present in the composition to a totalparts by weight of the partially hydrogenated thermoplastic elastomericblock copolymer present in the composition;

wherein the ratio III is ratio of a total parts by weight of theethylene-vinyl acetate copolymers present in the composition to a totalparts by weight of the partially hydrogenated thermoplastic elastomericblock copolymer present in the composition;

wherein the ratio IV is a ratio of the total parts by weight of thealpha-olefin linking polymers present in the composition to a totalparts by weight of the partially hydrogenated thermoplastic elastomericblock copolymer present in the composition, and

wherein the ratio V is a ratio of the total parts by weight of the oneor more ethylene-vinyl acetate copolymers present in the composition toa total parts by weight of the one or more olefinic copolymers presentin the composition.

11. The composition according to clause 10, wherein the sum of ratio I,II, III, IV, and V is from about 3.50 to about 5.00.

12. A composition comprising:

a partially hydrogenated thermoplastic elastomeric block copolymer, thepartially hydrogenated thermoplastic elastomeric block copolymercomprising:

-   -   one or more A blocks comprising aromatic repeat units,    -   one or more B blocks comprising aliphatic repeat units, and    -   one or more first ethylenically unsaturated groups present on        one or both of the aromatic repeat units and the aliphatic        repeat units;

an olefinic block copolymer, wherein the olefinic block copolymer is acopolymer of a first alpha-olefin and a second alpha-olefin differentfrom the first alpha-olefin, and wherein the olefinic block copolymercomprising one or more second ethylenically unsaturated groups;

an alpha-olefin linking polymer, wherein the alpha-olefin linkingpolymer comprises one or more aliphatic sidechains; and

an ethylene-vinyl acetate copolymer.

13. A composition comprising:

one or more partially hydrogenated thermoplastic elastomeric blockcopolymers, each of the one or more partially hydrogenated thermoplasticelastomeric block copolymers independently comprising one or morearomatic blocks, one or more aliphatic blocks, and one or more firstethylenically unsaturated units;

one or more olefinic block copolymers, each of the one or more olefinicblock copolymers comprising second ethylenically unsaturated units;

one or more alpha-olefin linking polymers; and

one or more ethylene-vinyl acetate copolymers;

wherein a sum of a ratio I, II, III, IV, and V is from about 1.00 toabout 10.00;

wherein the ratio I is a ratio of a total parts by weight of theolefinic block copolymers present in the composition to a total parts byweight of the partially hydrogenated thermoplastic elastomeric blockcopolymer present in the composition;

wherein the ratio II is a ratio of a total parts by weight of thealpha-olefin linking polymers present in the composition to a totalparts by weight of the partially hydrogenated thermoplastic elastomericblock copolymer present in the composition;

wherein the ratio III is ratio of a total parts by weight of theethylene-vinyl acetate copolymers present in the composition to a totalparts by weight of the partially hydrogenated thermoplastic elastomericblock copolymer present in the composition;

wherein the ratio IV is a ratio of the total parts by weight of thealpha-olefin linking polymers present in the composition to a totalparts by weight of the partially hydrogenated thermoplastic elastomericblock copolymer present in the composition, and

wherein the ratio V is a ratio of the total parts by weight of the oneor more ethylene-vinyl acetate copolymers present in the composition toa total parts by weight of the one or more olefinic copolymers presentin the composition.

14. The composition according to clause 13, wherein the sum of ratio I,II, III, IV, and V is from about 3.50 to about 5.00.

15. A composition comprising:

one or more partially hydrogenated thermoplastic elastomeric blockcopolymers, each of the one or more partially hydrogenated thermoplasticelastomeric block copolymers independently comprising one or morearomatic blocks, one or more aliphatic blocks, and one or more firstethylenically unsaturated units;

one or more olefinic block copolymers, each of the one or more olefinicblock copolymers comprising second ethylenically unsaturated units;

one or more alpha-olefin linking copolymers; and

one or more ethylene-vinyl acetate copolymers.

16. The composition according to any one of clauses 13-15, wherein thepartially hydrogenated thermoplastic elastomeric block copolymercomprises an A-B block structure or an A-B-A block structure,

wherein each of the A blocks comprise one or more aromatic repeat units,and

wherein the B block is an aliphatic polymer block comprising the one ormore first ethylenically unsaturated units.

17. The composition according to any one of clauses 10-16, wherein thepartially hydrogenated thermoplastic elastomeric block copolymercomprises about 10% to about 40% of the A block by weight based upon theweight of the partially hydrogenated thermoplastic elastomeric blockcopolymer.18. The composition according to any one of clauses 10-17, wherein thearomatic repeat units comprises styrenic repeat units.19. The composition according to any one of clauses 10-17, wherein thearomatic repeat units comprise an aliphatic backbone having a pluralityof aromatic side chains.20. The composition according to any one of clauses 10-19, wherein thealiphatic repeat units comprise one or more substituted or unsubstitutedalkyl side chains having about 2 to 18 carbon atoms.21. The composition according to any one of clauses 10-20, wherein theolefinic block copolymer is a copolymer of ethylene and the secondalpha-olefin.22. The composition according to any one of clauses 10-21, wherein thesecond alpha-olefin has 6 to 12 carbon atoms.23. The composition according to any one of clauses 10-22, wherein theolefinic block copolymer has one or more blocks rich in the firstalpha-olefin and one or more blocks rich in the second alpha-olefin24. The composition according to any one of clauses 1-23, wherein thecomposition comprises about 5 parts by weight to about 20 parts byweight of the A-B-A block copolymer or partially hydrogenatedthermoplastic elastomeric block copolymer based upon the total weight ofthe composition.25. The composition according to any one of clauses 1-24, wherein thecomposition comprises about 5 parts by weight to about 10 parts byweight of the A-B-A block copolymer or partially hydrogenatedthermoplastic elastomeric block copolymer based upon the total weight ofthe composition.26. The composition according to any one of clauses 1-25, wherein thecomposition comprises about 5 parts by weight to about 20 parts byweight of the olefinic block copolymer by weight based upon the totalweight of the composition.27. The composition according to any one of clauses 1-26, wherein thecomposition comprises about 10 parts by weight to about 15 parts byweight of the olefinic block copolymer by weight based upon the totalweight of the composition.28. The composition according to any one of clauses 1-27, wherein thecomposition comprises about 15 parts by weight to about 35 parts byweight of the alpha-olefin linking polymer based upon the total weightof the composition.29. The composition according to any one of clauses 1-28, wherein thecomposition comprises about 20 parts by weight to about 30 parts byweight of the alpha-olefin linking polymer based upon the total weightof the composition.30. The composition according to any one of clauses 1-29, wherein thecomposition comprises about 20 parts by weight to about 45 parts byweight of the ethylene-vinyl acetate copolymer based upon the totalweight of the composition.31. The composition according to any one of clauses 1-30, wherein thecomposition comprises about 30 parts by weight to about 40 parts byweight of the ethylene-vinyl acetate copolymer based upon the totalweight of the composition.32. The composition according to any one of clauses 1-31, furthercomprising one or both of a free-radical initiator and a chemicalblowing agent.33. The composition according to clause 32, further comprising thefree-radical initiator, and

wherein the free-radical initiator is selected from the group consistingof dicumyl peroxide; n-butyl-4,4-di(t-butylperoxy) valerate;1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane;2,5-dimethyl-2,5-di(t-butylperoxy) hexane; di-t-butyl peroxide;di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide;2,5-dimethyl-2,5-di(tbutylperoxy)hexyne-3;di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoylperoxide; t-butyl hydroperoxide; and a combination thereof.

34. The composition according to clause 32, further comprising thefree-radical initiator, and

wherein the free-radical initiator is selected from the group consistingof a peroxide, a diazo compound, and a combination thereof.

35. The composition according to clause 32, further comprising thechemical blowing agent,

wherein the chemical blowing agent is selected from the group consistingof a carbonate, bicarbonate, carboxylic acid, azo compound, isocyanate,persulfate, peroxide, and a combination thereof.

36. The composition according to any one of clauses 1-35, wherein aratio I of a total parts by weight of the olefinic copolymers present inthe composition to a total parts by weight of the A-B-A block copolymeror partially hydrogenated thermoplastic elastomeric block copolymerspresent in the composition is from about 0.65 to about 7.00.37. The composition according to any one of clauses 1-36, wherein aratio II of a total parts by weight of the linking polymers present inthe composition to a total parts by weight of the A-B-A block copolymeror partially hydrogenated thermoplastic elastomeric block copolymerspresent in the composition is from about 0.40 to about 3.50.38. The composition according to any one of clauses 1-37, wherein aratio III of a total parts by weight of the EVA copolymers present inthe composition to a total parts by weight of the A-B-A block copolymeror partially hydrogenated thermoplastic elastomeric block copolymerspresent in the composition is from about 1.00 to about 5.00.39. The composition according to any one of clauses 1-38, wherein aratio IV of a total parts by weight of the linking polymers present inthe composition to a total parts by weight of the A-B-A block copolymersor partially hydrogenated thermoplastic elastomeric block copolymerspresent in the composition is from about 3.50 to about 5.00.40. The composition according to any one of clauses 1-39, wherein aratio V of a total parts by weight of the one or more EVA copolymerspresent in the composition to a total parts by weight of the one or moreolefinic copolymers present in the composition is from about 2.00 toabout 5.00.41. The composition according to any one of clauses 1-40, wherein aratio VI of a total parts by weight of the one or more EVA copolymerspresent in the composition to a total parts by weight of the one or morelinking polymers present in the composition is from about 1.00 to about2.00.42. The composition according to any one of clauses 1-41, wherein theratio I is from about 0.8 to about 2.00.43. The composition according to any one of clauses 1-42, wherein theratio II is from about 1.00 to about 3.25.44. The composition according to any one of clauses 1-43, wherein theratio III is from about 3.50 to about 5.00.45. The composition according to any one of clauses 1-44, wherein a sumof ratio I, II, III, IV, and V is from about 1.00 to about 10.00.46. The composition according to any one of clauses 1-45, wherein a sumof ratio I, II, III, IV, and V is from about 3.50 to about 5.00.47. The composition according to any one of clauses 1-46, wherein a sumof ratio I, II, III, IV, V and VI is from about 1.50 to about 16.00.48. The composition according to any one of clauses 1-47, wherein a sumof ratio I, II, III, IV, V and VI is from about 14.00 to about 16.00.49. The composition according to any one of clauses 1-48, wherein theA-B-A block copolymer or the partially hydrogenated thermoplasticelastomeric block copolymers has an elongation at break of greater thanor equal to 650% as determined using ASTM D638.50. A partially crosslinked pre-foam composition, comprising a pre-foamcomposition according to any one of clauses 1-47 that has been reactedto a degree of crosslinking from about 50% to about 99%.51. A composition comprising a crosslinked reaction product of acomposition according to any one of clauses 1-49.52. A composition made by a process comprising crosslinking and foaminga composition according to any one of clauses 1-49.53. The composition according to clause 52, wherein the crosslinking andfoaming steps occur at about the same time.54. The composition according to clause 52 or clause 53, comprisinginjection molding the pre-foam composition into an injection mold andcrosslinking the pre-foam composition in the injection mold.55. The composition according to clause 54, wherein the injection moldis at a temperature from about 150° C. to about 190° C. during thecrosslinking.56. The composition according to any one of clauses 52-55, wherein thecomposition is compression molded to produce the foam composition.57. The composition according to any one of clauses 50-54, wherein theprocess further comprises annealing the foam article and thencompression molding the foam article, reducing it in size by at least10% in at least one dimension relative to its initial foamed and moldedstate prior to the compression molding.58. The composition according to any one of clauses 51-57, wherein thecomposition comprises a degree of crosslinking from about 50% to about99%.59. The composition according to any one of clauses 51-58, wherein thecomposition has a specific density of about 0.08 to about 0.15.60. The composition according to any one of clauses 51-59, wherein thecomposition has an energy return from about 60% to about 85%.61. The composition according to any one of clauses 51-60, wherein thecomposition has a split tear of about 1.6 kg/cm to about 4.0 kg/cm.62. The composition according to any one of clauses 51-61, wherein thecomposition has a split tear of about 2.5 kg/cm to about 3.5 kg/cm.63. The composition according to any one of clauses 51-62, wherein thecomposition has an Asker C hardness of about 40 to 60 C.64. A method of making a component for an article of footwear, themethod comprising foaming and crosslinking a composition according toany one of clauses 1-49.65. The method according to clause 64, wherein the crosslinking andfoaming steps occur at about the same time.66. The method according to clause 64, comprising injection molding thecomposition into an injection mold to form a foamed composition andcrosslinking the foamed composition in the injection mold.67. The method according to clause 66, wherein the injection mold is ata temperature from about 150° C. to about 190° C. during thecrosslinking.68. The method according to clause 66, wherein the foamed composition iscompression molded to produce the component.69. The method according to clause 68, further comprising annealing thefoamed composition and then compression molding the foamed composition,reducing it in size by at least 10% in at least one dimension relativeto its initial foamed and molded state prior to compression molding.70. A component for an article of footwear, the component comprising afoam composition according to any one of clauses 51-63.71. A component for an article of footwear, the component made by a by aprocess comprising injection molding and crosslinking a compositionaccording to any one of clauses 1-5072. The component according to clause 71, wherein the process furthercomprises compression molding the crosslinked composition to produce thecomponent.73. The component according to any one of clauses 70-72, wherein thecomponent is a midsole.74. The component according to any one of clauses 70-73, wherein thecomponent comprises a degree of crosslinking from about 50% to about99%.75. The component according to any one of clauses 70-74, wherein thecomponent has a specific density of about 0.08 to about 0.15.76. The component according to any one of clauses 70-75, wherein thecomponent has an energy return from about 60% to about 85%.77. The component according to any one of clauses 70-76, wherein thecomponent has a split tear of about 1.6 kg/cm to about 4.0 kg/cm.78. The component according to any one of clauses 70-77, wherein thecomponent has a split tear of about 2.5 kg/cm to about 3.5 kg/cm.79. The component according to any one of clauses 70-78, wherein thecomponent has an Asker C hardness of about 40 to 60 C.80. The component according to any one of clauses 70-79, wherein thearticle of footwear is a shoe.81. The component according to clause 80, wherein the shoe is selectedfrom the group consisting of an athletic shoe, a tennis shoe, across-trainer shoe, a children's shoe, a dress shoe, and a casual shoe.82. An article of footwear comprising a component according to any oneof clauses 70-81.83. The article of footwear according to clause 82, wherein the articleof footwear is a shoe, wherein the component is a midsole, and whereinthe shoe further comprises a shoe upper and a shoe outsole.84. A method of making an article of footwear, the method comprisingaffixing a component according to any one of clauses 70-81 to thearticle of footwear.85. The method according to clause 84, wherein the article of footwearis a shoe.86. The method according to clause 85, wherein the shoe is selected fromthe group consisting of an athletic shoe, a tennis shoe, a cross-trainershoe, a children's shoe, a dress shoe, and a casual shoe.87. The method according to clause 85 or clause 86, wherein thecomponent is a midsole and the method comprises affixing the midsole toone or both of a shoe upper and a shoe outsole.

I claim:
 1. An article of footwear comprising a component, wherein thecomponent is made by a process comprising crosslinking and foaming afirst composition, wherein the first composition comprises: a partiallyhydrogenated thermoplastic elastomeric block copolymer, the partiallyhydrogenated thermoplastic elastomeric block copolymer comprising: oneor more A blocks comprising aromatic repeat units, one or more B blockscomprising aliphatic repeat units, and one or more first ethylenicallyunsaturated groups present on one or both of the aromatic repeat unitsand the aliphatic repeat units; an olefinic block copolymer, wherein theolefinic block copolymer is a copolymer of a first alpha-olefin and asecond alpha-olefin different from the first alpha-olefin, wherein theolefinic block copolymer comprises one or more second ethylenicallyunsaturated groups, and wherein the olefinic block copolymer is acopolymer of ethylene and an alpha-olefin having about 6 to 12 carbonatoms; and an ethylene-vinyl acetate copolymer; wherein a ratio I isfrom about 0.65 to about 7.00; wherein the ratio I is a ratio of a totalparts by weight of the olefinic block copolymer present in the firstcomposition to a total parts by weight of the partially hydrogenatedthermoplastic elastomeric block copolymer present in the firstcomposition.
 2. The article of footwear according to claim 1, whereinthe component is a midsole.
 3. The article of footwear according toclaim 1, wherein the first composition comprises about 5 parts by weightto about 20 parts by weight of the partially hydrogenated thermoplasticelastomeric block copolymer.
 4. The article of footwear according toclaim 1, wherein the first composition comprises about 5 parts by weightto about 20 parts by weight of the olefinic block copolymer.
 5. Thearticle of footwear according to claim 1, wherein the first compositionfurther comprises one or both of a free-radical initiator and a chemicalblowing agent.
 6. The article of footwear according to claim 1, whereinthe component has an energy return of about 60 percent to about 85percent.
 7. The article of footwear according to claim 1, wherein theratio I is about 0.65 to 2.00.
 8. The article of footwear according toclaim 1, wherein the ratio I is about 1.00 to about 3.00.
 9. The articleof footwear according to claim 1, wherein the olefinic block copolymerdoes not comprise a cycloalkyl olefin.
 10. The article of footwearaccording to claim 1, wherein the ethylene-vinyl acetate copolymer has avinyl acetate content of about 10 percent to about 45 percent by weightbased upon the weight of the ethylene-vinyl acetate copolymer.
 11. Thearticle of footwear according to claim 1, wherein a ratio V is fromabout 2.50 to 4.50; and wherein the ratio V is a ratio of the totalparts by weight of the one or more ethylene-vinyl acetate copolymerspresent in the first composition to a total parts by weight of theolefinic block copolymer present in the first composition.
 12. Thearticle of footwear according to claim 1, wherein the first compositioncomprises about 30 parts by weight to about 60 parts by weight of theethylene-vinyl acetate copolymer.
 13. The article of footwear accordingto claim 1, wherein the component has an energy return of about 70percent to about 85 percent.
 14. The article of footwear according toclaim 1, wherein the first composition further comprises an alpha-olefinlinking polymer, wherein the alpha-olefin linking polymer comprises oneor more aliphatic sidechains.
 15. The article of footwear according toclaim 14, wherein the alpha-olefin linking polymer is a copolymer ofethylene and an alpha-olefin having about 3 to 8 carbon atoms, andwherein the alpha-olefin linking polymer has an alpha-olefin monomercontent of about 15 percent to about 40 percent by weight based upon theweight of the alpha-olefin linking polymer.
 16. The article of footwearaccording to claim 1, wherein each of the aromatic repeat units of the Ablocks of the partially hydrogenated thermoplastic elastomeric blockcopolymer comprise aliphatic backbones having a plurality of aromaticside chains.
 17. The article of footwear according to claim 1, whereinthe partially hydrogenated thermoplastic elastomeric block copolymer hasan elongation at break of greater than 650 percent when measured usingASTM D638.
 18. The article of footwear according to claim 1, wherein thepartially hydrogenated thermoplastic elastomeric block copolymer is aPS_(q)-X¹ _(n)-X² _(m)-X³ _(p) block copolymer; wherein PS representspolystyrene; X¹ is a poly-C₂-C₈-alkylene; X² is a poly-C₂-C₈-alkylene;and X³ is polyether, polyester, polycarbonate, polyamide, polyketone orpolysiloxane; wherein the subscripts q, n, m, and p represent molefractions such that 1>q>0, n is 0 to 1, m is 0 to 1, and p is 0 to 1 solong as q+n+m+p=1.
 19. The article of footwear according to claim 1,wherein the ethylene-vinyl acetate copolymer comprises a first ethylenevinyl acetate copolymer and a second ethylene vinyl acetate copolymer;wherein the first ethylene vinyl acetate copolymer comprises about 15mole percent to about 40 mole percent vinyl acetate; and wherein thesecond ethylene vinyl acetate copolymer comprises about 15 mole percentto about 30 mole percent vinyl acetate.